GB2202224A - Benzodioxole derivative useful as an intermediate - Google Patents
Benzodioxole derivative useful as an intermediate Download PDFInfo
- Publication number
- GB2202224A GB2202224A GB08807566A GB8807566A GB2202224A GB 2202224 A GB2202224 A GB 2202224A GB 08807566 A GB08807566 A GB 08807566A GB 8807566 A GB8807566 A GB 8807566A GB 2202224 A GB2202224 A GB 2202224A
- Authority
- GB
- United Kingdom
- Prior art keywords
- compound
- benzodioxole
- formula
- preparation
- derivative useful
- 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
- 150000005528 benzodioxoles Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LJGCAWPZURVJEZ-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxole-4-carboxamide Chemical compound NC(=O)C1=CC=CC2=C1OC(F)(F)O2 LJGCAWPZURVJEZ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- DBUAYOWCIUQXQW-UHFFFAOYSA-N 1,3-benzodioxole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=C1OCO2 DBUAYOWCIUQXQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RXIKYXZKSIARLN-UHFFFAOYSA-N 2,2-difluoro-1,3-benzodioxol-4-amine Chemical compound NC1=CC=CC2=C1OC(F)(F)O2 RXIKYXZKSIARLN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- -1 benzodioxole compound Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 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
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
- A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
- A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
- A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
CHEMICAL COMPOUND
The present invention relates to a novel benzodioxole compound and its preparation. The novel compound is a valuable intermediate for the synthesis of biocidal compounds.
Accordingly the present invention provides the compound of formula I
The compound is prepared by Hofmann degradation, i.e. by reacting 2,2-difluoro-4-carbamoyl-1 ,3-benzodioxole with bromine, in the presence of aqueous alkali metal hydroxide.
CONH2 NH2 t3C X Br2 X; ( I ) O F hydroxide O F hydroxide This process is carried out in accordance with the method of
L.M. Yagupolskii et al., Zhur. Obshch. Khym. 31, 628 (1981).
The precursors for the preparation of the compound of formula I are synthesised as follows starting from 4-carboxy-1,3benzodioxole (in accordance with W.H. Perkin and V.M. Trikojus,
J. Chem. Soc. 1926, 2925):
The compound of the present invention is particularly useful for preparing the compound of formula II
by reacting the compound of formula I with the compound of formula III
in the presence of an acid acceptor in an inert solvent or diluent.
The compound of formula (II) its preparation and use are described and claimed in copending application No. 8607566 (Serial No. 2173793).
The invention is illustrated in more detail by the follwoing
Examples.
Example 1.1
Preparation of 2,2-difluoro-4-amino-1,3-benzodioxole
52.5g of bromine are added dropwise at 0 C to a solution of 120g of potassium hydroxide in 780 ml of water. Subsequently, 50.8g of 2,2-difluoro-4-carbamoyl-1,3-benzodioxole are added, and the reaction mixture is stirred for 30 minutes at room temperature and then heated for 45 minutes to 800C. The reaction solution is then diluted in 400 ml of water and distilled with steam. The distillate is extracted with diethyl ether and dried over sodium sulfate. The solvent is evaporated off, affording 38.1g of the title compund as a yellowish oil with a refractive index nD21 of 1.4955.
Example 1.2:
Preparation of 2,2-dichloro-4-carbonyl chloride-1 ,3-benzodioxole
40g of 4-carboxy-1,3-benzodioxole are mixed with 150g of phosphorus pentachloride, and the mixture is heated to 70"C.
After 3.5 hours, the temperature is increased to 900C and then held at this level of 12 hours. Subsequently, the volatile components are distilled off at 110C and 2000 Pa, and the residue is distilled off under high vacuum, affording 45g of the title compound as a slightly yellowish solid.
Example 1.3
Preparation of 2,2-difluoro-4-carbonyl fluoride 1 ,3-benzodioxole
In a distillation apparatus, 55.7g of SbF3 are added to 59.4g of 2,2-dichloro-4-carbonyl chloride 1 ,3-benzodioxole, whereupon a reaction takes place immediately. In-order to maintain the reaction, the temperature is slowly increased, while simultaneously gradually evacuating. 59.5g of a red oil distill over at 105-1170C and 6666 Pa. The distillate is taken up in 100 ml of diethyl ether and washed with two 150 ml portions of semiconcentrated hydrochloric acid and then with water. The ether solution is dried over sodium sulfate and the solvent is evaporated off, affording 42.0g of the title compound.
Example 1.4
Preparation of 2,2-difluoro-4-carbamoyl-1 ,3-benzodioxole
With ice cooling and stirring, 63.6g of a 2,2-difluoro4-carbonyl fluoride-1,3-benzodioxole are added dropwise to 120 ml of a concentrated 25 % solution of ammonia. In the course of several hours a crystalline slurry is formed which is then isolated by filtration and washed in succession with a dilute solution of ammonia and then with water, affording 51g of 2,2-difluoro-4-carbamoyl-1,3-benzodioxole with a melting point of 129.5-131"C.
Claims (3)
1. The compound of formula I
2. A process for the preparation of the compound of formula I, which process comprises subjecting the compound of the formula
to Hofmann degradation with bromine, in the presence of aqueous alkali metal hydroxide.
3. A process according to claim 2 substantially as hereinbefore described with reference to foregoing Example 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH143485 | 1985-04-03 | ||
| GB08607566A GB2173793B (en) | 1985-04-03 | 1986-03-26 | Pesticidal compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8807566D0 GB8807566D0 (en) | 1988-05-05 |
| GB2202224A true GB2202224A (en) | 1988-09-21 |
| GB2202224B GB2202224B (en) | 1989-01-25 |
Family
ID=25687637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08807566A Expired GB2202224B (en) | 1985-04-03 | 1986-03-26 | Benzodioxole derivative useful as an intermediate |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2202224B (en) |
-
1986
- 1986-03-26 GB GB08807566A patent/GB2202224B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2202224B (en) | 1989-01-25 |
| GB8807566D0 (en) | 1988-05-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930326 |