WO1991001977A1 - Verfahren zur herstellung von 2,6-dichlorchinoxalin - Google Patents
Verfahren zur herstellung von 2,6-dichlorchinoxalin Download PDFInfo
- Publication number
- WO1991001977A1 WO1991001977A1 PCT/EP1990/001162 EP9001162W WO9101977A1 WO 1991001977 A1 WO1991001977 A1 WO 1991001977A1 EP 9001162 W EP9001162 W EP 9001162W WO 9101977 A1 WO9101977 A1 WO 9101977A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chloro
- hydroxyquinoxaline
- approximately
- oxide
- sodium salt
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 17
- WFOKVKYNVKVWFK-UHFFFAOYSA-N 2,6-dichloroquinoxaline Chemical compound N1=C(Cl)C=NC2=CC(Cl)=CC=C21 WFOKVKYNVKVWFK-UHFFFAOYSA-N 0.000 claims abstract description 15
- PIABSKIGZJHDAO-UHFFFAOYSA-N ClC=1C=C2N=CC(=[N+](C2=CC1)[O-])O Chemical compound ClC=1C=C2N=CC(=[N+](C2=CC1)[O-])O PIABSKIGZJHDAO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000012320 chlorinating reagent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 239000012442 inert solvent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- SJAZZQLTKBYDHN-UHFFFAOYSA-N 6-chloro-1h-quinoxalin-2-one Chemical compound C1=C(Cl)C=CC2=NC(O)=CN=C21 SJAZZQLTKBYDHN-UHFFFAOYSA-N 0.000 claims description 11
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011814 protection agent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SPSSDDOTEZKOOV-UHFFFAOYSA-N 2,3-dichloroquinoxaline Chemical compound C1=CC=C2N=C(Cl)C(Cl)=NC2=C1 SPSSDDOTEZKOOV-UHFFFAOYSA-N 0.000 description 1
- LTHQFFWUHBKRGG-UHFFFAOYSA-N 3-chloro-1h-quinoxalin-2-one Chemical class C1=CC=C2N=C(Cl)C(O)=NC2=C1 LTHQFFWUHBKRGG-UHFFFAOYSA-N 0.000 description 1
- RNOLFZACEWWIHP-UHFFFAOYSA-N 6-chloro-1,4-dihydroquinoxaline-2,3-dione Chemical compound N1C(=O)C(=O)NC2=CC(Cl)=CC=C21 RNOLFZACEWWIHP-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 241001233037 catfish Species 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/50—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to ring nitrogen atoms
- C07D241/52—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
Definitions
- the invention relates to an improved process compared to the prior art for the preparation of 2,6-dichloroquinoxaline by reducing 6-chloro-2-hydroxyquinoxaline-N-oxide to 6-chloro-2-hydroxyquinoxaline, crystallizing its sodium salt, removing the Water and chlorination in a manner known per se.
- 2,6-dichloroquinoxaline is an important intermediate for the production of crop protection agents (EP 276 741A; DE-OS 30 04 770). It is important that the 2,6-dichloroquinoxaline is used in pure form. All known processes for the preparation of 2,6-dichloroquinoxaline (cf. EP 0 295 815; EP 0 295 797; USP 4,636,562; Sakata et al., Heterocycles £ 3, 143, 2025 (1985); DE 3 901 406; European patent application 89 106 784.5, in conjunction with Houben-Weyl, Vol. VIII, 359 ff.
- 2,6-dichloroquinoxaline can be prepared in high purity and at the same time in very good yield by using 6-chloro-2-hydroxyquinoxaline N-oxide in aqueous sodium hydroxide solution in the presence of about 0.001 to about 0.5 mol percent, preferably 0.01 to about 0.05 mol percent of a platinum coated catalyst, based on the 6-chloro-2-hydroxyquinoxaline-N-oxide used, at temperatures of about 20 to about 120 ° C., preferably of about 60 up to about 100 ⁇ C, at a hydrogen pressure of about 1 to about 100 bar, preferably from about 5 to about 20 bar, with about 1 to about 3 equivalents of sodium hydroxide, based on 6-chloro-2-hydroxyquinoxaline-N-oxide, are present, hydrogenated, after separating the catalyst from the hot solution, the 6-chloro-2-hydroxyquinoxaline dissolved therein by cooling the reaction solution to a temperature of about 0 to about 20 ° C., preferably
- the 6-chloro-2-hydroxyquinoxaline-N-oxide in the aqueous sodium hydroxide solution in a concentration of about 15 to about 30 percent by weight, preferably from about 20 to about 25 percent by weight, in the form of the hydrogenation subject.
- the catalytic hydrogenation increases as a function of reaction parameters, for about 30 minutes to about 5 hours, usually about '* l to about 3 hours.
- Shell catalysts are hydrogenation catalysts in which the noble metal, for example platinum, is in its finest form and is predominantly distributed on the surface of a carrier material particle, for example activated carbon, in contrast to what is usually to be designated Precious metal catalysts that have a predominantly uniform distribution of the noble metal also within (via pores, etc.) of a carrier material particle.
- the noble metal for example platinum
- a carrier material particle for example activated carbon
- the catalyst used can be used repeatedly.
- the sodium salt of 6-chloro-2-hydroxyquinoxaline formed by the hydrogenation is in solution under the reaction conditions and can be easily separated from the catalyst. Upon subsequent cooling to about 0 to about 20 ° C, preferably about 5 to about 10 ° C, it is practically quantitative. The product thus obtained is of excellent quality.
- an inert diluent which can form an azeotrope with water.
- suitable diluents are benzene, toluene, xylenes (all isomers and their mixtures), cumene, chlorobenzene, ethylbenzene, carbon tetrachloride, trichloromethane, cyclohexane, hexane, heptane and suitable petroleum ether fractions. Then the water contained is separated off azeotropically.
- the 6-chloro-2-hydroxyquinoxaline obtained at the end of the hydrogenation stage in high purity and in very good yield as such, it can be added to the separated sodium salt by adding a mineral acid such as sulfuric or hydrochloric acid 6-chloro-2 * -hydroxyquinoxaline or preferably to an * aqueous solution of this compound in simple catfish be kept pure.
- a mineral acid such as sulfuric or hydrochloric acid 6-chloro-2 * -hydroxyquinoxaline or preferably to an * aqueous solution of this compound in simple catfish be kept pure.
- a dried sample of the sodium salt showed the following
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19893925969 DE3925969A1 (de) | 1989-08-05 | 1989-08-05 | Verfahren zur herstellung von 2,6-dichlorchinoxalin |
| DEP3925969.2 | 1989-08-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1991001977A1 true WO1991001977A1 (de) | 1991-02-21 |
Family
ID=6386594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1990/001162 WO1991001977A1 (de) | 1989-08-05 | 1990-07-16 | Verfahren zur herstellung von 2,6-dichlorchinoxalin |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPH04507406A (enrdf_load_stackoverflow) |
| CA (1) | CA2064564A1 (enrdf_load_stackoverflow) |
| DE (1) | DE3925969A1 (enrdf_load_stackoverflow) |
| IN (1) | IN169080B (enrdf_load_stackoverflow) |
| WO (1) | WO1991001977A1 (enrdf_load_stackoverflow) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345831C (zh) * | 2005-11-10 | 2007-10-31 | 吴永虎 | 高纯度2,6－二氯喹喔啉的制备方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914069A (zh) * | 2010-07-29 | 2010-12-15 | 安徽丰乐农化有限责任公司 | 6-氯-2-羟基喹喔啉的氯化新工艺 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636562A (en) * | 1982-05-07 | 1987-01-13 | E. I. Du Pont De Nemours And Company | Process for preparing 6-halo-2-chloroquinoxaline |
| EP0295815A2 (en) * | 1987-06-19 | 1988-12-21 | UNIROYAL CHEMICAL COMPANY, Inc. | Process for production of 2-quinoxalines |
| EP0295797A2 (en) * | 1987-06-19 | 1988-12-21 | UNIROYAL CHEMICAL COMPANY, Inc. | Process for the selective reduction of 2-quinoxaline-4-oxides |
-
1989
- 1989-08-05 DE DE19893925969 patent/DE3925969A1/de not_active Withdrawn
-
1990
- 1990-07-16 CA CA 2064564 patent/CA2064564A1/en not_active Abandoned
- 1990-07-16 WO PCT/EP1990/001162 patent/WO1991001977A1/de not_active Application Discontinuation
- 1990-07-16 JP JP2510679A patent/JPH04507406A/ja active Pending
- 1990-07-18 IN IN601/CAL/90A patent/IN169080B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4636562A (en) * | 1982-05-07 | 1987-01-13 | E. I. Du Pont De Nemours And Company | Process for preparing 6-halo-2-chloroquinoxaline |
| EP0295815A2 (en) * | 1987-06-19 | 1988-12-21 | UNIROYAL CHEMICAL COMPANY, Inc. | Process for production of 2-quinoxalines |
| EP0295797A2 (en) * | 1987-06-19 | 1988-12-21 | UNIROYAL CHEMICAL COMPANY, Inc. | Process for the selective reduction of 2-quinoxaline-4-oxides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345831C (zh) * | 2005-11-10 | 2007-10-31 | 吴永虎 | 高纯度2,6－二氯喹喔啉的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04507406A (ja) | 1992-12-24 |
| CA2064564A1 (en) | 1991-02-06 |
| DE3925969A1 (de) | 1991-02-07 |
| IN169080B (enrdf_load_stackoverflow) | 1991-08-31 |
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