CN108203415A - A kind of method for preparing benzene pyrazoles humulone - Google Patents
A kind of method for preparing benzene pyrazoles humulone Download PDFInfo
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- CN108203415A CN108203415A CN201611187348.1A CN201611187348A CN108203415A CN 108203415 A CN108203415 A CN 108203415A CN 201611187348 A CN201611187348 A CN 201611187348A CN 108203415 A CN108203415 A CN 108203415A
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- China
- Prior art keywords
- pyrazoles humulone
- benzene pyrazoles
- methyl
- preparation
- methylsulphur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
Abstract
The invention discloses a kind of methods for preparing benzene pyrazoles humulone, the process employs chloroacetic chlorides and 3 (2 methyl, 6 methylsulphur base phenyl) 4,5 dihydro-isoxazoles react, 3 (2 methyl, 6 methylsulphur base phenylacetyls) 4 of generation, 5 dihydro-isoxazoles generate 3 (2 methyl, 6 methylsulphur yl benzoic acids) 4 by iodoform reaction, 5 dihydro-isoxazoles, then prepare benzene pyrazoles humulone with the condensation rearrangement of 1 methyl, 5 hydroxypyrazoles.The preparation method provided by the invention for preparing benzene pyrazoles humulone key intermediate, overcome the shortcomings that carbon monoxide severe toxicity gas difficulty operates in carbon monoxide insert row method, the shortcomings that required bromine water is hypertoxic in bromination process is also overcomed simultaneously, the shortcomings that needing reaction temperature low, have many advantages, such as it is at low cost, easy to operate, pollution less, safety and environmental protection, be suitble to large-scale production.
Description
Technical field
A kind of present invention design organic synthesis field, and in particular to method for preparing benzene pyrazoles humulone.
Background technology
[2- methyl -3- (4,5 dihydro -3- isoxazoles) -4- (methyl sulphonyl) phenyl]-(5- hydroxyl -1- methyl-1 H- pyrroles
Azoles -4- bases) ketone (Topramezone) topramezone, (the general entitled Topramezone of CAS210631-68-8, ISO),
Chemical structural formula is as follows：
Benzene pyrazoles humulone be BASF Aktiengesellschaft find and the structure of exploitation in, while include pyrazole ring He isoxazole ring
P-hydroxybenzene pyruvic acid (HPP) ester dual oxide enzyme (4-HPPD) inhibitor of 2 kinds of structures, 4-HPPD inhibitor is the 1990s
Determining new herbicide target.It is by inhibiting the 4- hydroxyl base phenylacetone acid esters dual oxide enzymes of plastoquinone biosynthesis
(HPPD), so as to inhibit the synthesis of class flower radish element indirectly, chloroplaset complex functionality under light illumination is interfered, it is dead to eventually lead to weeds
It dies.Since mechanism of action of the HPPD in animal and plant body is different, so it is safe to animal.Benzene pyrazoles humulone is to be so far
The only less and safer a kind of herbicide of active highest, dosage.
Benzene pyrazoles humulone can be used for cauline leaf process after corn field seedling, be a kind of broad weed-killing spectrum, applied widely, safety
The herbicide of high, function and effect soon, with other herbicide good compatibilities.Broad weed-killing spectrum is shown to milpa annual gramineae
And broad leaved weed, such as lady's-grass, eleusine indica, bald barnyard, Mazus japonicus, smallflower galinsoga herb, concave head amaranth, sand-grass of cracking rice, flat fringe nutgrass flatsedge, piemarker
Annual grassy weeds and spontaneous Brassica campestris L seedling have good effect, the luxuriant grass of malignant weed such as acalypha copperleaf, meal, triquetrousc murdannia herb etc., can be gone with green bristlegrass
90% wettable powder 50g of Tianjin is used with, can reach good herbicidal effect；Use scope is removed after extensively showing general maize seedling
Careless agent can only use in the corn 2-6 leaf phases, have apparent poisoning more than this phase medication, benzene pyrazoles humulone usage time range is more
Extensively；In addition benzene pyrazoles humulone is other than general corn, to corn, waxy corn and pop corn safety higher, therefore, benzene
Pyrazoles humulone is considered as all corn herbicide safeties best one kind both at home and abroad currently on the market；Along with its effect
Speed is fast, shows 2-5 days significant effects of medication, and good compatibility, can be with atrazine, nicosulfuron, primisulfuronmethyl and isopropyl
Alachlor is used in mixed way, and obtains preferable effect.So 2009 defend listing in Chinese commodity name when benzene pyrazoles humulone with bud,
Its market reaction is positive, and with nicosulfuron, mesotrione is stood like the legs of a tripod, and is widely applied rapidly at home, it has also become corn
The mainstream kind of field herbicidal, there is good market prospects.
It is domestic at present that the mechanism of action, field are concentrated mainly on to the research of benzene pyrazoles humulone by a large amount of literature survey
Using safety research, the research of separation and the quantitative analysis of active compound, the document in relation to synthesizing is less, German BASF pair
The synthesis of benzene pyrazoles humulone did patent and reported for work (patent No. WO2008059370A2).BASF AG reports two completely
Route and several possible routes.
Wherein report that the complete route total recovery of above-mentioned item reaches 20%, but multistep needs high pressure and heating equipment, also
The noble metal catalysts such as Metal Palladium, Jin Shu Bo need to be used, these catalyst are expensive, and recycling is difficult, and totle drilling cost is high.Technique road
In line, 3- (2- methyl -6- methylsulphurs yl benzoic acid) -4, the preparation of 5 dihydro-isoxazoles is a most difficult step：Its industrially prepared side
Method is mainly carbon monoxide insert row method, but this method yield is relatively low, and the severe toxicity one used in carbon monoxide insert row method aoxidizes
Carbon gas, while taller temperature high pressure, it is also necessary to which expensive palladium metal composite catalyst, production cost is high, and operation difficulty is big, no
Meet the requirement of large-scale production.
Invention content
A kind of benzene pyrazoles humulone key intermediate 3- (2- methyl -6- methylsulphur bases phenylacetyl) -4, the preparation of 5 dihydro-isoxazoles
Method includes the following steps：
Ⅰ
In the step, the ratio of the chloroacetic chloride and chemical compounds I is 1-5:1.
In the step, the reaction temperature of the chloroacetic chloride and chemical compounds I is -20 DEG C -120 DEG C, reaction time 1-14
Hour.
In the step, reaction dissolvent is hexane, and hexamethylene is run quickly, toluene, dichloroethanes, 1,2 dichloroethanes, chloroform, 1,
4 dioxane, ether, one kind or arbitrary proportion mixed solvent in tetrahydrofuran.
In the step, the weight ratio of solvent for use and chemical compounds I is 2-8:1.
In the step, catalyst needed for the reacting of the chloroacetic chloride and chemical compounds I is alchlor, stannous chloride, three
Iron chloride etc..
In the step, the molar ratio 1-8 of used catalyst and chemical compounds I:1.
The invention discloses a kind of benzene pyrazoles humulone key intermediate 3- (2- methyl -6- methylsulphur bases phenylacetyl) -4,5 dihydros
The preparation method of isoxazole, the process employs chloroacetic chlorides and 3- (2- methyl -6- methylsulphur bases phenyl) -4, and 5 dihydro-isoxazoles are anti-
Should, the 3- (2- methyl -6- methylsulphur bases phenylacetyl) -4 of generation, 5 dihydro-isoxazoles generate 3- (2- methyl -6- by iodoform reaction
Methylsulphur yl benzoic acid) -4,5 Er Qing Yi Evil oxazoles, then prepare benzene pyrazoles humulone with the condensation rearrangement of -5 hydroxy-pyrazole of 1- methyl.This
The preparation method for preparing benzene pyrazoles humulone key intermediate provided is provided, it is acute to overcome carbon monoxide in carbon monoxide insert row method
The shortcomings that poisonous gas difficulty operates, while the shortcomings that required bromine water in bromination process is hypertoxic is also overcomed, need reaction temperature low
Shortcoming, have many advantages, such as it is at low cost, easy to operate, pollution less, safety and environmental protection, be suitble to large-scale production.
It is provided by the invention to prepare benzene pyrazoles humulone key intermediate 3- (2- methyl -6- methylsulphur bases phenylacetyl) -4,5 dihydros
The preparation method of isoxazole, reaction yield is high, and production is more economical.
Specific embodiment：
Clear, complete description will be carried out to the technology in the embodiment of the present invention below, it is clear that described embodiment is only
Only it is the part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiment in invention, ordinary skill
Personnel obtain every other embodiment under the premise of no creative work, belong to the scope of the present invention.
Embodiment 1
Step:Take 5mol (1195g) 3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles, the 1 of 10L, 2 dichloros
Ethane is added in reactor, is cooled to 0 DEG C, adds in the alchlor of 6mol (800g), 5mol chloroacetic chlorides are added dropwise at 0 DEG C
(392.5g) maintains to react at 0 DEG C of reaction temperature.After insulation reaction 2h, water is added in, is filtered, is washed again, be spin-dried for solvent, is done
It is dry, compound ii is obtained, weigh 1190g, yield 85%, content 98%.
Embodiment 2
Step:Take 5mol (1195g) 3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles, the Isosorbide-5-Nitrae epoxy of 10L
Six rings are added in reactor, are cooled to 0 DEG C of key intermediate, add in the alchlor of 6mol (800g), 5mol is added dropwise at 0 DEG C
Chloroacetic chloride (392.5g) maintains to react at 0 DEG C of reaction temperature.After insulation reaction 2h, water is added in, is filtered, is washed, be spin-dried for molten again
Agent, it is dry, compound ii is obtained, weigh 1190g, yield 85%, content 98%.
Embodiment 3
Step:Take 5mol (1195g) 3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles, the tetrahydrofuran of 10L
It is added in reactor, is cooled to 0 DEG C, add in the alchlor of 6mol (800g), 5mol chloroacetic chlorides are added dropwise at 0 DEG C
(392.5g) maintains to react at 0 DEG C of reaction temperature.After insulation reaction 2h, water is added in, is filtered, is washed again, be spin-dried for solvent, is done
It is dry, compound ii is obtained, weigh 1250g, yield 89%, content 98%.
Embodiment 4
Step:5mol (1195g) 3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles are taken, the toluene of 10L adds in
Into reactor, 0 DEG C is cooled to, the alchlor of 6mol (800g) is added in, 5mol chloroacetic chloride (key intermediates is added dropwise at 0 DEG C
Key intermediate 392.5g), it maintains to react at 0 DEG C of reaction temperature.After insulation reaction 2h, water is added in, filters, washes again, is revolved
Dry solvent, it is dry, compound ii is obtained, weigh 1263g, yield 90%, content 98%.
Solvent in above-mentioned steps can also be benzene, hexamethylene, dimethylbenzene, dichloromethane, chloroform, ether, wait it is a kind of or
Person is a variety of.
Embodiment 5
On the basis of embodiment 1, the technical characteristics such as " add in water, filter, wash again " in step are changed to " take out
Filter is washed again ", other technical characteristics are constant, obtain compound ii, and weigh 1190g, yield 85%, content 98%.
Embodiment 6
Step:Take 5mol (1195g) 3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles, the Isosorbide-5-Nitrae epoxy of 10mL
Six rings are added in reactor, are cooled to 0 DEG C, add in the alchlor of 6mol (800g), 5mol chloroacetic chlorides are added dropwise at 0 DEG C
(392.5g) maintains to react at 5 DEG C of reaction temperature.After insulation reaction 2h, water is added in, is filtered, is washed again, be spin-dried for solvent, is done
It is dry, compound ii is obtained, weigh 1278g, yield 91%, content 98%.
Embodiment 7
On the basis of embodiment 1, insulation reaction is revised as reacting at 5 DEG C, and other technical characteristics are constant, obtain chemical combination
Object II, weigh 1190g, yield 85%, content 98%.
Embodiment 8
Step:Take 5mol (1195g) 3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles, the 1 of 10L, 2 dichloros
Ethane is added in reactor, is cooled to dropwise addition 5mol chloroacetic chlorides at 0 DEG C, stannous chloride 7.5mol (1691g), 0 DEG C
(392.5g) maintains to react at 0 DEG C of reaction temperature.After insulation reaction 2h, water is added in, is filtered, is washed again, be spin-dried for solvent, is done
It is dry, compound ii is obtained, weigh 1334g, yield 95%, content 98%.The foregoing is merely preferred embodiments of the present invention, and
Not to limit this patent, all any modifications made within the scope of the present invention, equivalent replacement etc., this should be included in
In the protection domain of patent.
Claims (7)
- A kind of 1. method for preparing benzene pyrazoles humulone, which is characterized in that required preparation method includes the following steps：3- (2- methyl -6- methylsulphur bases phenyl) -4,5 dihydro-isoxazoles are reacted with chloroacetic chloride at a certain temperature, catalyst Effect is lower to react, and generates 3- (2- methyl -6- methylsulphur bases phenylacetyl) -4,5 dihydro-isoxazole.
- 2. the preparation method of benzene pyrazoles humulone key intermediate according to claim 1, which is characterized in that the chloroacetic chloride Ratio with chemical compounds I is 1-5:1.
- 3. the preparation method of benzene pyrazoles humulone according to claim 1, which is characterized in that the chloroacetic chloride and chemical compounds I Reaction temperature for -20 DEG C -120 DEG C, the reaction time is 1-14 hours.
- 4. the preparation method of benzene pyrazoles humulone according to claim 1, which is characterized in that reaction dissolvent is n-hexane, ring Hexane, benzene, toluene, 1,2 dichloroethanes, chloroform, Isosorbide-5-Nitrae dioxane, ether, one kind or arbitrary proportion mixing in tetrahydrofuran Solvent.
- 5. the preparation method of benzene pyrazoles humulone according to claim 4, which is characterized in that solvent for use and chemical compounds I Weight ratio is 2-8:1.
- 6. the preparation method of benzene pyrazoles humulone according to claim 1, which is characterized in that the chloroacetic chloride and chemical compounds I Reaction needed for catalyst be alchlor, stannous chloride, ferric trichloride.
- 7. the preparation method of benzene pyrazoles humulone according to claim 1, which is characterized in that used catalyst and chemical compounds I Molar ratio 1-8:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117750C (en) * | 1997-01-17 | 2003-08-13 | 巴斯福股份公司 | 3-heterocyclyl-substituted benzoyl derivatives |
| CN104292137A (en) * | 2014-10-15 | 2015-01-21 | 武汉工程大学 | Process for synthesizing triketone herbicide cyclic sulcotrione |
-
2016
- 2016-12-20 CN CN201611187348.1A patent/CN108203415A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117750C (en) * | 1997-01-17 | 2003-08-13 | 巴斯福股份公司 | 3-heterocyclyl-substituted benzoyl derivatives |
| CN104292137A (en) * | 2014-10-15 | 2015-01-21 | 武汉工程大学 | Process for synthesizing triketone herbicide cyclic sulcotrione |
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