CN108947873A - 2-(3,3,3- trifluoro propyl) benzsulfamide preparation method - Google Patents
2-(3,3,3- trifluoro propyl) benzsulfamide preparation method Download PDFInfo
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- CN108947873A CN108947873A CN201810988997.4A CN201810988997A CN108947873A CN 108947873 A CN108947873 A CN 108947873A CN 201810988997 A CN201810988997 A CN 201810988997A CN 108947873 A CN108947873 A CN 108947873A
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- benzsulfamide
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- acrylic
- reduction reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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Abstract
The invention discloses a kind of 2-(3,3,3- trifluoro propyls) preparation method of benzsulfamide, it is 3, the 3- tri- fluoro- 1- acrylic by 2-(3) benzsulfamide obtains through reduction reaction；Reduction reaction is carried out in the presence of magnesium rod and methanol.The fluoro- 1- acrylic of 2-(3,3,3- tri-) molar ratio of benzsulfamide and magnesium rod is 1: 1~1: 3；The fluoro- 1- acrylic of 2-(3,3,3- tri-) weight ratio of benzsulfamide and methanol is 1: 3~1: 10；Reduction reaction temperature is 10~60 DEG C；The reduction reaction time is 1~5h.The present invention uses magnesium rod+Reduction of methanol reduction system 2-(3,3,3- tri- fluoro- 1- acrylic) benzsulfamide, lower production costs simple compared to precious metal catalyst hydroprocessing.The present invention can obtain higher reaction yield and product purity by optimizing to reaction condition, be suitble to industrialized production.
Description
Technical field
The invention belongs to herbicide intermediate preparation technical fields, and in particular to a kind of prosulfuron intermediate 2-(3,3,3-
Trifluoro propyl) benzsulfamide preparation method.
Background technique
The chemical name of prosulfuron (also referred to as prosulfuron) is 1- (4- methoxyl group -6- methyl-1,3,5- triazine -2-
Base) -3- [2- (3,3,3- trifluoro propyl) benzene sulfonyl] urea, it is mainly used for preventing and kill off broadleaf weeds, to abutilon, Amaranthus, Chenopodium, knotweed
The weeds such as category, Stellaria have excellent preventive effect.Suitable for crop such as corn, sorghum, cereal crop, lawn and pasture.Because of it
Half-life period in the soil is 8~40d, and the half-life period in plant is 1~2.5h, hence it is evident that shorter than other commercialization sulphonyl
Metabolism time of the carbamide herbicides in plant.To seeding corn and other crops safety, to succession crop for example barley, wheat, oat,
Rice, soybean, potato influence less, but generate phytotoxicity sometimes to sweet tea Lay, sunflower.It is mainly used for postemergence weed control, uses
Dosage is 10~40g(a.i.)/ha.It, can also further expansion herbicidal spectrum if mixing application with having its herbicide.
2-(3,3,3- trifluoro propyls) benzsulfamide then be synthesize prosulfuron important intermediate, for the system of the intermediate
Standby, prior art discloses following two methods:
Method one: Chinese patent literature CN101597246A is disclosed with the chloro- 4-(3,3,3- trifluoro propyl of 1,2- bis-) benzene is
Starting material, sulfonated, ammonification obtain the chloro- 2-(3 of 4,5- bis-, 3,3- trifluoro propyls) benzsulfamide, then hydrogen is catalyzed through palladium carbon
Change obtains 2-(3,3,3- trifluoro propyl) benzsulfamide.
Method two: american documentation literature US4671819 is disclosed with the fluoro- 1- acrylic of 2-(3,3,3- tri-) benzsulfamide is
Starting material directly obtains 2-(3,3,3- trifluoro propyls through palladium carbon catalytic hydrogenation) benzsulfamide.
One synthetic route of method is longer, and total recovery is lower, and palladium carbon catalytic hydrogenation is complicated for operation, and production cost is higher.
Two synthetic route of method is shorter, and yield is higher, but there are still palladium carbon catalytic hydrogenation is complicated for operation, production cost
Higher defect.
Summary of the invention
The purpose of the present invention is to solve the above problem, provides one kind easy to operate, lower production costs 2-(3, and 3,3-
Trifluoro propyl) benzsulfamide preparation method.
Realize the object of the invention technical solution be: a kind of 2-(3,3,3- trifluoro propyls) benzsulfamide preparation method,
It is by the fluoro- 1- acrylic of 2-(3,3,3- tri-) benzsulfamide obtains through reduction reaction；It is characterized by: the reduction reaction is
It is carried out in the presence of magnesium rod and methanol.
The 2-(3,3,3- tri- fluoro- 1- acrylic) molar ratio of benzsulfamide and the magnesium rod is 1: 1~1: 3, preferably
It is 1: 2.
The 2-(3,3,3- tri- fluoro- 1- acrylic) weight ratio of benzsulfamide and the methanol is 1: 3~1: 10, preferably
It is 1: 5.
The reduction reaction temperature is 10~60 DEG C, preferably 30~40 DEG C.
The reduction reaction time is 1~5h, preferably 2h.
In order to obtain higher reaction yield and product purity, the 2-(3,3,3- tri- fluoro- 1- acrylic) benzsulfamide
Molar ratio with the magnesium rod is 1: 2~1: 3；The fluoro- 1- acrylic of the 2-(3,3,3- tri-) benzsulfamide and the methanol
Weight ratio is 1: 5；The reduction reaction temperature is 30~40 DEG C；The reduction reaction time is 2~5h.
In order to obtain highest reaction yield and product purity, the 2-(3,3,3- tri- fluoro- 1- acrylic) benzsulfamide
Molar ratio with the magnesium rod is 1: 2；The fluoro- 1- acrylic of the 2-(3,3,3- tri-) benzsulfamide and the methanol weight ratio
It is 1: 5；The reduction reaction temperature is 30~40 DEG C；The reduction reaction time is 2h.
The good effect that the present invention has:
(1) present invention uses the fluoro- 1- acrylic of magnesium rod+Reduction of methanol reduction system 2-(3,3,3- tri-) benzsulfamide preparation 2-
(3,3,3- trifluoro propyl) benzsulfamide, lower production costs simple compared to precious metal catalyst hydroprocessing.
(2) present invention can obtain higher reaction yield (95% or more) and product by optimizing to reaction condition
Purity (95%) is suitble to industrialized production.
Specific embodiment
(embodiment 1)
The 2-(3,3,3- trifluoro propyl of the present embodiment) benzsulfamide preparation method it is specific as follows:
The methanol of 400g and the fluoro- 1- acrylic of 2-(3,3,3- tri- of 80g are added in four mouthfuls of reaction flasks of 1L) benzsulfamide
(0.32mol), is warming up to 30~40 DEG C, and at this temperature, magnesium rod is added portionwise in control, and every 30min adds once, every time plus 1.5g,
Altogether plus 10 times (total 15g, 0.625mol), last time, 30~40 DEG C of insulation reaction 2h are added.
After reaction, it is evaporated under reduced pressure methanol, until there are a large amount of solids to be precipitated, temperature is no more than 50 DEG C, and distillation terminates, and is added
300g toluene is cooled to 10 DEG C hereinafter, the dilute hydrochloric acid of 10wt% is added dropwise, and adjusting pH=4~5 have adjusted stirring 30min, have been warming up to 50
~60 DEG C, toluene layer is cooled to 5~10 DEG C by layering, and product is precipitated, and filters, obtains 77.0g faint yellow solid, yield is
95.5%, purity 97.7%(HPLC).
(2~embodiment of embodiment 5)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Magnesium rod | 15g | 7.7g | 23g | 15g | 15g |
| Methanol | 400g | 400g | 400g | 240g | 800g |
| Yield | 77.0g | 72.6g | 76.6g | 70.2g | 72.6g |
| Yield | 95.5% | 90.0% | 95.0% | 87.1% | 90.0% |
| Purity | 97.7% | 86.3% | 97.2% | 90.5% | 95.6% |
(6~embodiment of embodiment 9)
The preparation method of each embodiment is substantially the same manner as Example 1, and difference is shown in Table 2.
Table 2
| Embodiment 1 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | |
| Temperature | 30~40 DEG C | 10℃ | 60℃ | 30~40 DEG C | 30~40 DEG C |
| Time | 2h | 2h | 2h | 1h | 5h |
| Yield | 77.0g | 60.5g | 63.7g | 68.5g | 76.6g |
| Yield | 95.5% | 75.0% | 79.0% | 84.9% | 95.0% |
| Purity | 97.7% | 80.6% | 93.2% | 89.5% | 96.1% |
Claims (7)
1. a kind of 2-(3,3,3- trifluoro propyls) preparation method of benzsulfamide, it is 3, the 3- tri- fluoro- 1- acrylic by 2-(3)
Benzsulfamide is obtained through reduction reaction；It is characterized by: the reduction reaction is carried out in the presence of magnesium rod and methanol.
2. 2-(3 according to claim 1,3,3- trifluoro propyls) preparation method of benzsulfamide, it is characterised in that: it is described
The fluoro- 1- acrylic of 2-(3,3,3- tri-) molar ratio of benzsulfamide and the magnesium rod is 1: 1~1: 3.
3. 2-(3 according to claim 1,3,3- trifluoro propyls) preparation method of benzsulfamide, it is characterised in that: it is described
The fluoro- 1- acrylic of 2-(3,3,3- tri-) weight ratio of benzsulfamide and the methanol is 1: 3~1: 10.
4. 2-(3 according to claim 1,3,3- trifluoro propyls) preparation method of benzsulfamide, it is characterised in that: it is described
Reduction reaction temperature is 10~60 DEG C.
5. 2-(3 according to claim 1,3,3- trifluoro propyls) preparation method of benzsulfamide, it is characterised in that: it is described
The reduction reaction time is 1~5h.
6. 2-(3 according to one of claims 1 to 5,3,3- trifluoro propyls) preparation method of benzsulfamide, feature exists
In the 2-(3,3,3- tri- fluoro- 1- acrylic) molar ratio of benzsulfamide and the magnesium rod is 1: 2~1: 3；The 2-(3,
The fluoro- 1- acrylic of 3,3- tri-) weight ratio of benzsulfamide and the methanol is 1: 5；The reduction reaction temperature is 30~40 DEG C；
The reduction reaction time is 2~5h.
7. 2-(3 according to one of claims 1 to 5,3,3- trifluoro propyls) preparation method of benzsulfamide, feature exists
In the 2-(3,3,3- tri- fluoro- 1- acrylic) molar ratio of benzsulfamide and the magnesium rod is 1: 2；The 2-(3,3,3- tri-
Fluoro- 1- acrylic) weight ratio of benzsulfamide and the methanol is 1: 5；The reduction reaction temperature is 30~40 DEG C；It is described to go back
The former reaction time is 2h.
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| CN201810988997.4A CN108947873A (en) | 2018-08-28 | 2018-08-28 | 2-(3,3,3- trifluoro propyl) benzsulfamide preparation method |
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| CN201810988997.4A CN108947873A (en) | 2018-08-28 | 2018-08-28 | 2-(3,3,3- trifluoro propyl) benzsulfamide preparation method |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4671819A (en) * | 1983-03-28 | 1987-06-09 | Ciba-Geigy Corporation | N-phenylsulfonyl-N'-triazinylureas |
| CN104788347A (en) * | 2015-03-23 | 2015-07-22 | 大连奇凯医药科技有限公司 | Method for preparing 2-(trifluoromethoxy) benzene sulfonamide |
-
2018
- 2018-08-28 CN CN201810988997.4A patent/CN108947873A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4671819A (en) * | 1983-03-28 | 1987-06-09 | Ciba-Geigy Corporation | N-phenylsulfonyl-N'-triazinylureas |
| CN104788347A (en) * | 2015-03-23 | 2015-07-22 | 大连奇凯医药科技有限公司 | Method for preparing 2-(trifluoromethoxy) benzene sulfonamide |
Non-Patent Citations (3)
| Title |
|---|
| G. H. LEE ET AL.: "Magnesium in Methanol (Mg/MeOH) in Organic Syntheses", 《CURRENT ORGANIC CHEMISTRY》 * |
| ROBERT O. HUTCHINS ET AL.: "Selective Reductions of Conjugated Acetylenes with Magnesium in Methanol and Methanol-D", 《TETRAHEDRON LETTERS》 * |
| 尹志刚: "《有机化学》", 28 February 2010, 河南科学技术出版社 * |
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