CN105906591A - Synthesis method of 2-amino-gamma-butyrolactone hydrochloride - Google Patents
Synthesis method of 2-amino-gamma-butyrolactone hydrochloride Download PDFInfo
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- CN105906591A CN105906591A CN201610268551.5A CN201610268551A CN105906591A CN 105906591 A CN105906591 A CN 105906591A CN 201610268551 A CN201610268551 A CN 201610268551A CN 105906591 A CN105906591 A CN 105906591A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 ring carbon atoms
- C07D307/66—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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 ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention discloses a synthesis method of 2-amino-gamma-butyrolactone hydrochloride (I) for a kind of important chemical, dye, pesticide and medical intermediates. The synthesis method includes the following steps: taking a gamma-butyrolactone compound (II) and a nitroso ester compound (III) as raw materials to react with each other to obtain 2-(hydroxyl imino)-gamma-butyrolactone (IV), and subjecting the compound (IV) to reduction reaction and acidification to obtain the 2-amino-gamma-butyrolactone hydrochloride (I). The method used for preparing the product compound (I) is mild in condition, simple to operate, high in yield, low in environmental pollution, easier for industrial production and the like.
Description
Technical field
The present invention relates to the preparation method of glufosinate-ammonium intermediate, particularly relate to 2-amino-gamma-butyrolacton hydrochlorate (I)
The new preparation method of preparation method.
Technical background
2-amino-gamma-butyrolacton hydrochlorate (I) can be as the key intermediate of glufosinate-ammonium synthesis.Glufosinate-ammonium was 20th century
A kind of herbicide that first eighties is produced by Heochst company of Germany.It has that anti-grass spectrum is wide, low toxicity, efficient, non-selective
Etc. advantage, it it is a kind of organic phosphates steriland herbicide with part systemic action.
Three big herbicide kinds are glyphosate, N,N'-dimethyl-.gamma..gamma.'-dipyridylium and glufosinate-ammonium the most in the world.Large area, big due to glyphosate
Amount is reused, and the resistance problem already leading to weeds is difficult to solve.And it is only second to the world's second largest herbicide hundred of glyphosate
Grass is withered, because causing the most unproductive being poisoned to death and not having antidote, N,N'-dimethyl-.gamma..gamma.'-dipyridylium will exit city in 1 day July in 2016
?.So glufosinate-ammonium just obtains huge development space.The advantage such as the strong activity of weeding of glufosinate-ammonium, broad weed-killing spectrum, poisoning are little and
The extensively plantation of glufosinate-resistant transgenic crop makes this kind generation of glufosinate-ammonium be attracted attention.But owing to technique, environmental protection etc. are asked
Topic puzzlement, the production capacity of China's glufosinate-ammonium remains in about 1000 tons, does not has the company of large-scale production glufosinate-ammonium.
Most manufacturers all use Strecker method to synthesize glufosinate-ammonium.Strecker method technical maturity,
Reaction condition is less demanding, and yield can reach about 35%.This route conditions is gentle, stable yield, is the most ripe
One of glufosinate-ammonium route.But, this method inevitably to use severe toxicity cyanide, gives to produce and causes potential safety with environment
Threaten.At present agriculture chemical registration just towards efficient, high-load, low toxicity, noresidue, without security risk, without environmental risk, nothing use wind
Direction, danger is developed.So how get around Strecker method, propose that a kind of route is short, yield is high, safety is high, it is little to pollute, be suitable for
The preparation method of industrialized production glufosinate-ammonium is significant.
There are reports for the method for synthesis 2-amino-gamma-butyrolacton hydrochlorate (I), (Koch, Troels;
Buchardt, Ole.Synthesis, 1993,11,1065-1067): it is raw material with methionine, obtains through three steps synthesis.
Document report yield 60%, this route cost is the highest, and the response time is the longest and introduces poisonous reagent iodomethane, it is difficult to
Detection reaction process.
Summary of the invention
The invention provides one and prepare the new method of 2-amino-gamma-butyrolacton class hydrochlorate (I), use this law to prepare
Product I, not only mild condition, simple to operate, yield is high, and it is little to have environmental pollution, is more easy to realize industrialized production etc.
Advantage.As the intermediate of glufosinate-ammonium synthesis, this law effectively avoids the extremely toxic substances such as cyanide, the industrialization to glufosinate-ammonium
Production has reference value.
The method preparing 2-amino-gamma-butyrolacton class hydrochlorate (I) that the present invention provides, is divided into following steps:
(1) with gamma-butyrolacton compounds (II) and nitrite compounds (III) as raw material, it is dissolved in organic solvent,
Add alkali, obtain 2-(oxyimino)-gamma-butyrolacton (IV) in-70 DEG C-25 DEG C reaction 1-6h.Gamma-butyrolacton compounds
(II) mol ratio with nitrite compounds (III) is 1: 0.5~1: 1.5, preferably 1: 1~1.2;Reactant II and alkali
Mol ratio be 1: 0.5~1: 2.5, preferably 1: 1.2~1.5.
R1 structure representation is: H, substituted or non-substituted straight chain, side chain or ring-type alkyl, phenyl, benzyl, Wherein m=1~8.Above-mentioned straight chain, side chain or ring-type alkyl can tables further
State as (1) C1~C10Alkyl: methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, amyl group, new
Amyl group, hexyl, heptyl, octyl group;(2)C3~C10Cycloalkyl: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl;(3)C3~C10Alkene
Base: pi-allyl, cyclobutenyl, crotyl, pentenyl, pentenyl, 3-pentenyl;(4)C3~C10Alkynyl: propinyl, butine
Base, 2-butyne base, pentynyl, valerylene base, 3-pentynyl;Substituted-phenyl can be addressed further under as (1) 2-fluorophenyl, 3-fluorine
Phenyl, 4-fluorophenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl,
3-iodophenyl, 4-iodophenyl (2) 2-tolyl, 3-tolyl, 4-tolyl;(3) 2-anisyl, 3-anisyl, 4-first
Oxygen phenyl, 2,3-dimethoxy phenyl, 2,4-dimethoxy phenyl, 2,5-dimethoxy phenyl, 2,6-dimethoxy phenyl, 3,4,5-front threes
Oxygen phenyl;(4) 2-acetyl phenyl, 3-acetyl phenyl, 4-acetyl phenyl, 2-propionylphenyl, 3-propionylphenyl, 4-propionylphenyl,
2-butyryl phenyl, 3-butyryl phenyl, 4-butyryl phenyl, 2-valeryl phenyl, 3-valeryl phenyl, 4-valeryl phenyl;(5) 2-Nitrobenzol
Base, 3-nitrobenzophenone, 4-nitrobenzophenone, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-hydroxy phenyl, 3-hydroxy benzenes
Base, 4-hydroxy phenyl, 2-carboxyl phenyl, 3-carboxyl phenyl, 4-carboxyl phenyl;Substituted benzyl can be addressed further under as (1) 2-fluorine
Benzyl, 3-luorobenzyl, 4-luorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl,
2-iodine benzyl, 3-iodine benzyl, 4-iodine benzyl;(2) 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl;(3) 2-methoxybenzyl,
3-methoxybenzyl, 4-methoxybenzyl, 2,3-veratryl, 2,4-veratryl, 2,5-veratryl, 2,6-dimethoxy
Benzyl, 3,4,5-trimethoxy benzyls;(4) 2-acetyl benzyl, 3-acetyl benzyl, 4-acetyl benzyl, 2-propionyl benzyl, 3-propionyl benzyl
Base, 4-propionyl benzyl, 2-butyryl benzyl, 3-butyryl benzyl, 4-butyryl benzyl, 2-valeryl benzyl, 3-valeryl benzyl, 4-valeryl benzyl
Base;(5) 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-aminobenzyl, 3-aminobenzyl, 4-aminobenzyl, 2-hydroxyl
Base benzyl, 3-hydroxybenzyl, 4-hydroxybenzyl, 2-carboxybenzyl, 3-carboxybenzyl, 4-carboxybenzyl.
R2Structure representation is: H, COOR6, CONR6R7, (CH2)nXR6(wherein, n=1~8), XR6.X is O, NH, NR7, S.
Wherein, R6、R7Can be expressed as: represent hydrogen, substituted or non-substituted straight chain, side chain or ring-type alkyl, phenyl, benzyl,Wherein m=1~8,1-naphthyl, 2-naphthyl, furan or pyranoid form five, hexa-atomic sugar
Base or replace glycosyl, or 2~5 by different way (such as: 1,2-, Isosorbide-5-Nitrae-, 1,6-) glucosyl group that connects or replace glucose
Base.Above-mentioned straight chain, side chain or ring-type alkyl can be addressed further under as (1) C1~C10Alkyl: methyl, ethyl, propyl group, isopropyl
Base, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, amyl group, neopentyl, hexyl, heptyl, octyl group;(2)C3~C10Cycloalkyl: ring
Propyl group, cyclobutyl, cyclopenta, cyclohexyl;(3)C3~C10Thiazolinyl: pi-allyl, cyclobutenyl, crotyl, pentenyl, 2-amylene
Base, 3-pentenyl;(4)C3~C10Alkynyl: propinyl, butynyl, 2-butyne base, pentynyl, valerylene base, 3-pentynyl;Take
Can be expressed as phenyl: (1) 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromine
Phenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl;(2) 2-tolyl, 3-tolyl, 4-toluene
Base, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl;(3) 2-anisyl, 3-methoxy benzene
Base, 4-anisyl, 2,3-dimethoxy phenyl, 2,4-dimethoxy phenyl, 2,5-dimethoxy phenyl, 2,6-dimethoxy phenyl, 3,
4,5-2,4,5-trimethoxyphenyls;(4) 2-acetyl phenyl, 3-acetyl phenyl, 4-acetyl phenyl, 2-propionylphenyl, 3-propionylphenyl, 4-third
Acyl phenyl, 2-butyryl phenyl, 3-butyryl phenyl, 4-butyryl phenyl, 2-valeryl phenyl, 3-valeryl phenyl, 4-valeryl phenyl;(5)
2-nitrobenzophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-hydroxy phenyl,
3-hydroxy phenyl, 4-hydroxy phenyl, 2-carboxyl phenyl, 3-carboxyl phenyl, 4-carboxyl phenyl;Substituted benzyl can be addressed further under
For: (1) 2-luorobenzyl, 3-luorobenzyl, 4-luorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl
Base, 4-bromobenzyl, 2-iodine benzyl, 3-iodine benzyl, 4-iodine benzyl;(2) 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl, 2,
3-dimethyl benzyl, 2,4-dimethyl benzyl, 2,5-dimethyl benzyl, 2,6-dimethyl benzyl;(3) 2-methoxybenzyl, 3-first
Oxygen benzyl, 4-methoxybenzyl, 2,3-veratryl, 2,4-veratryl, 2,5-veratryl, 2,6-dimethoxy benzyl
Base, 3,4,5-trimethoxy benzyls;(4) 2-acetyl benzyl, 3-acetyl benzyl, 4-acetyl benzyl, 2-propionyl benzyl, 3-propionyl benzyl
Base, 4-propionyl benzyl, 2-butyryl benzyl, 3-butyryl benzyl, 4-butyryl benzyl, 2-valeryl benzyl, 3-valeryl benzyl, 4-valeryl benzyl
Base;(5) 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-aminobenzyl, 3-aminobenzyl, 4-aminobenzyl, 2-hydroxyl
Base benzyl, 3-hydroxybenzyl, 4-hydroxybenzyl, 2-carboxybenzyl, 3-carboxybenzyl, 4-carboxybenzyl.
R3Structure representation is: H, substituted or non-substituted straight chain, side chain or ring-type alkyl, phenyl, benzyl, Wherein m=1~8.Above-mentioned straight chain, side chain or ring-type alkyl can tables further
State as (1) C1~C10Alkyl: methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, amyl group, new
Amyl group, hexyl, heptyl, octyl group;(2)C3~C10Cycloalkyl: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl;(3)C3~C10Alkene
Base: pi-allyl, cyclobutenyl, crotyl, pentenyl, pentenyl, 3-pentenyl;(4)C3~C10Alkynyl: propinyl, butine
Base, 2-butyne base, pentynyl, valerylene base, 3-pentynyl.
Alkali can be potassium tert-butoxide (sodium), Sodium ethylate (potassium), Feldalat NM (potassium), triethylamine, potassium carbonate, sodium carbonate, cesium carbonate,
Calcium hydride, sodium hydride.It is preferably potassium tert-butoxide.
Organic solvent is in acetone, butanone, the alcohol of C1-C4, acetonitrile, oxolane, DMF or DMSO and above several are molten
The mixed solvent of agent composition is carried out.It is preferably DMF.
(2) the compound IV prepared in step 1 is passed through reduction reaction again, then in the ethyl acetate solution of hydrogen chloride
Acidifying obtains 2-amino-gamma-butyrolacton hydrochlorate (I).
In step 2, reducing agent is 5% or 10% palladium carbon;Raney's nickel;Sodium borohydride (potassium).
In step 2, the palladium carbon of reactant IV and 5% or 10% and the mass ratio of Raney's nickel be: 20~5: 1, is preferably
10∶1;Reactant IV with sodium borohydride (potassium) ratio is: 1: 1~10.
In step 2, reaction is in acetone, butanone, the alcohol of C1-C4, acetonitrile, oxolane and above several solvents forms
Mixed solvent in carry out.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, its objective is to be better understood on this
Bright substantive distinguishing features, therefore the cited case is not construed as the restriction to invention protection domain of the present invention.
Embodiment 1
In 500ml single port bottle, being sequentially added into gamma-butyrolacton 10g, nitrous acid straight butyl 13.2g, after DMF150ml.Cooling
To-30 DEG C, it is slowly added to potassium tert-butoxide 19.55g in batches, keeps temperature less than-10 DEG C to reaction completely.Tlc detects reaction
The reaction of raw material gamma-butyrolacton completely, adds 10ml water and 10ml acetic acid cancellation reaction, and decompression is distilled off major part solvent, its
Middle DMF recoverable.After adding 100ml water, ethyl acetate aqueous layer extracted 3 times, washing once, is dried and is spin-dried for.EA recrystallization,
Obtain product 10.3g, yield 75%.
1HNMR (300M, DMSO): 12.65 (s, 1H, OH), 4.44-4.49 (t, 2H, OCH2), 2.93-2.98 (t, 2H,
CH2)
Embodiment 2
In 100ml single port bottle, it is sequentially added into 2g 2-(oxyimino)-gamma-butyrolacton, 0.2g10% wet palladium carbon, 30ml
Methanol and 3ml glacial acetic acid, react 4h, temperature 40 DEG C in nitrogen atmosphere.Completely, suction filtered through kieselguhr, palladium carbon can return in tlc monitoring reaction
Receive.Decompression is distilled off solvent and obtains water white transparency oily thing, is added thereto to 100ml hydrogen chloride/ethyl acetate saturated solution,
Stirring 0.5h, sucking filtration, it is dried.Obtain product 2.3g, productivity 96%.
1HNMR (300M, D2O): 2.40-2.81 (m, 2H, CH2), 3.68-3.89 (m, 1H, CHCOO), 4.33-4.61 (m,
2H, OCH2)。
Claims (11)
- The preparation method of 1.2-(oxyimino)-gamma-butyrolacton (IV): reacted by compound II and compound III, generationization Compound IV.WhereinR1Structure representation is: H, substituted or non-substituted straight chain, side chain or ring-type alkyl, phenyl, benzyl, Wherein m=1~8.Above-mentioned straight chain, side chain or ring-type alkyl can be addressed further under as (1) C1 ~C10Alkyl: methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, amyl group, neopentyl, hexyl, Heptyl, octyl group;(2)C3~C10Cycloalkyl: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl;(3)C3~C10Thiazolinyl: pi-allyl, fourth Thiazolinyl, crotyl, pentenyl, pentenyl, 3-pentenyl;(4)C3~C10Alkynyl: propinyl, butynyl, 2-butyne base, Pentynyl, valerylene base, 3-pentynyl;Substituted-phenyl can be addressed further under as (1) 2-fluorophenyl, 3-fluorophenyl, 4-fluorobenzene Base, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4- Iodophenyl (2) 2-tolyl, 3-tolyl, 4-tolyl;(3) 2-anisyl, 3-anisyl, 4-anisyl, 2,3- Dimethoxy phenyl, 2,4-dimethoxy phenyl, 2,5-dimethoxy phenyl, 2,6-dimethoxy phenyl, 3,4,5-2,4,5-trimethoxyphenyls;(4) 2-acetyl phenyl, 3-acetyl phenyl, 4-acetyl phenyl, 2-propionylphenyl, 3-propionylphenyl, 4-propionylphenyl, 2-butyryl phenyl, 3-butyryl phenyl, 4-butyryl phenyl, 2-valeryl phenyl, 3-valeryl phenyl, 4-valeryl phenyl;(5) 2-nitrobenzophenone, 3-Nitrobenzol Base, 4-nitrobenzophenone, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy benzenes Base, 2-carboxyl phenyl, 3-carboxyl phenyl, 4-carboxyl phenyl;Substituted benzyl can be addressed further under as (1) 2-luorobenzyl, 3-fluorine benzyl Base, 4-luorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-iodine benzyl, 3- Iodine benzyl, 4-iodine benzyl;(2) 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl;(3) 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2,3-veratryl, 2,4-veratryl, 2,5-veratryl, 2,6-veratryl, 3,4,5- Trimethoxy benzyl;(4) 2-acetyl benzyl, 3-acetyl benzyl, 4-acetyl benzyl, 2-propionyl benzyl, 3-propionyl benzyl, 4-propionyl benzyl Base, 2-butyryl benzyl, 3-butyryl benzyl, 4-butyryl benzyl, 2-valeryl benzyl, 3-valeryl benzyl, 4-valeryl benzyl;(5) 2-nitre Base benzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-aminobenzyl, 3-aminobenzyl, 4-aminobenzyl, 2-hydroxybenzyl, 3-hydroxyl Base benzyl, 4-hydroxybenzyl, 2-carboxybenzyl, 3-carboxybenzyl, 4-carboxybenzyl.R2Structure representation is: H, COOR6, CONR6R7, (CH2)nXR6(wherein, n=1~8), XR6.X is O, NH, NR7, S.Wherein, R6、R7Can be expressed as: represent hydrogen, substituted or non-substituted straight chain, side chain or ring-type alkyl, phenyl, benzyl,Wherein m=1~8,1-naphthyl, 2-naphthyl, furan or pyranoid form five, hexa-atomic sugar Base or replace glycosyl, or 2~5 by different way (such as: 1,2-, Isosorbide-5-Nitrae-, 1,6-) glucosyl group that connects or replace glucose Base.Above-mentioned straight chain, side chain or ring-type alkyl can be addressed further under as (1) C1~C10Alkyl: methyl, ethyl, propyl group, isopropyl Base, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, amyl group, neopentyl, hexyl, heptyl, octyl group;(2)C3~C10Cycloalkyl: ring Propyl group, cyclobutyl, cyclopenta, cyclohexyl;(3)C3~C10Thiazolinyl: pi-allyl, cyclobutenyl, crotyl, pentenyl, 2-amylene Base, 3-pentenyl;(4)C3~C10Alkynyl: propinyl, butynyl, 2-butyne base, pentynyl, valerylene base, 3-pentynyl;Take Can be expressed as phenyl: (1) 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorphenyl, 3-chlorphenyl, 4-chlorphenyl, 2-bromine Phenyl, 3-bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl;(2) 2-tolyl, 3-tolyl, 4-toluene Base, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl;(3) 2-anisyl, 3-methoxy benzene Base, 4-anisyl, 2,3-dimethoxy phenyl, 2,4-dimethoxy phenyl, 2,5-dimethoxy phenyl, 2,6-dimethoxy phenyl, 3, 4,5-2,4,5-trimethoxyphenyls;(4) 2-acetyl phenyl, 3-acetyl phenyl, 4-acetyl phenyl, 2-propionylphenyl, 3-propionylphenyl, 4-third Acyl phenyl, 2-butyryl phenyl, 3-butyryl phenyl, 4-butyryl phenyl, 2-valeryl phenyl, 3-valeryl phenyl, 4-valeryl phenyl;(5) 2-nitrobenzophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 2-hydroxy phenyl, 3-hydroxy phenyl, 4-hydroxy phenyl, 2-carboxyl phenyl, 3-carboxyl phenyl, 4-carboxyl phenyl;Substituted benzyl can be addressed further under For: (1) 2-luorobenzyl, 3-luorobenzyl, 4-luorobenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl Base, 4-bromobenzyl, 2-iodine benzyl, 3-iodine benzyl, 4-iodine benzyl;(2) 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl, 2, 3-dimethyl benzyl, 2,4-dimethyl benzyl, 2,5-dimethyl benzyl, 2,6-dimethyl benzyl;(3) 2-methoxybenzyl, 3-first Oxygen benzyl, 4-methoxybenzyl, 2,3-veratryl, 2,4-veratryl, 2,5-veratryl, 2,6-dimethoxy benzyl Base, 3,4,5-trimethoxy benzyls;(4) 2-acetyl benzyl, 3-acetyl benzyl, 4-acetyl benzyl, 2-propionyl benzyl, 3-propionyl benzyl Base, 4-propionyl benzyl, 2-butyryl benzyl, 3-butyryl benzyl, 4-butyryl benzyl, 2-valeryl benzyl, 3-valeryl benzyl, 4-valeryl benzyl Base;(5) 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-aminobenzyl, 3-aminobenzyl, 4-aminobenzyl, 2-hydroxyl Base benzyl, 3-hydroxybenzyl, 4-hydroxybenzyl, 2-carboxybenzyl, 3-carboxybenzyl, 4-carboxybenzyl.R3Structure representation is: H, substituted or non-substituted straight chain, side chain or ring-type alkyl, phenyl, benzyl, Wherein m=1~8.Above-mentioned straight chain, side chain or ring-type alkyl can be addressed further under as (1) C1 ~C10Alkyl: methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl, amyl group, neopentyl, hexyl, Heptyl, octyl group;(2)C3~C10Cycloalkyl: cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl;(3)C3~C10Thiazolinyl: pi-allyl, fourth Thiazolinyl, crotyl, pentenyl, pentenyl, 3-pentenyl;(4)C3~C10Alkynyl: propinyl, butynyl, 2-butyne base, Pentynyl, valerylene base, 3-pentynyl.
- 2. the preparation method described in claim 1, wherein the mol ratio of reactant II and reactant III is 1: 0.5~1: 1.5.
- 3. the preparation method described in claim 1, alkali can be potassium tert-butoxide (sodium), Sodium ethylate (potassium), Feldalat NM (potassium), three second Amine, potassium carbonate, sodium carbonate, cesium carbonate, calcium hydride, sodium hydride.
- 4. the preparation method described in claim 1, the mol ratio of reactant II and alkali is 1: 0.5~1: 2.5.
- 5. the preparation method described in claim 1, react acetone, butanone, the alcohol of C1-C4, acetonitrile, oxolane, DMF or Carry out in DMSO and in the mixed solvent of above several solvents composition.
- 6. the preparation method described in claim 1, reaction temperature therein is-70 DEG C~25 DEG C.
- The preparation method of 7.2-amino-gamma-butyrolacton hydrochlorate (I):Carried out reduction reaction and acidifying by compound IV, generate compound I.
- 8. the preparation method described in claim 7, reducing agent is the palladium carbon of 5% or 10%;Raney's nickel;Sodium borohydride (potassium).
- 9. the preparation method described in claim 7, the dry palladium carbon of reactant IV and 5% or 10% and the mass ratio of Raney's nickel For: 20~5: 1;Reactant IV with sodium borohydride (potassium) ratio is: 1: 1~10.
- 10. the preparation method described in claim 9, reaction in acetone, butanone, the alcohol of C1-C4, acetonitrile, oxolane and The mixed solvent of above several solvents composition is carried out.
- Preparation method described in 11. claim 7, reaction temperature therein is 0 DEG C~80 DEG C.
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CN109232644A (en) * | 2018-09-30 | 2019-01-18 | 武汉工程大学 | The synthetic method of glufosinate-ammonium |
US11834441B2 (en) | 2019-12-06 | 2023-12-05 | Vertex Pharmaceuticals Incorporated | Substituted tetrahydrofurans as modulators of sodium channels |
US11919887B2 (en) | 2019-12-06 | 2024-03-05 | Vertex Pharmaceuticals Incorporated | Substituted tetrahydrofurans as modulators of sodium channels |
US11827627B2 (en) | 2021-06-04 | 2023-11-28 | Vertex Pharmaceuticals Incorporated | N-(hydroxyalkyl (hetero)aryl) tetrahydrofuran carboxamides as modulators of sodium channels |
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