CN101824144A - Polyethylene glycol aryloxyacetate, preparation thereof and application as plant growth regulator - Google Patents
Polyethylene glycol aryloxyacetate, preparation thereof and application as plant growth regulator Download PDFInfo
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- CN101824144A CN101824144A CN 201010175189 CN201010175189A CN101824144A CN 101824144 A CN101824144 A CN 101824144A CN 201010175189 CN201010175189 CN 201010175189 CN 201010175189 A CN201010175189 A CN 201010175189A CN 101824144 A CN101824144 A CN 101824144A
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Abstract
The invention provides a series of compounds with biological activity-polyethylene glycol aryloxyacetate and a preparation method thereof, belonging to the technical field of chemical synthesis. The preparation method comprises the steps of firstly using chloroacetyl chloride and polyethylene glycol to carry out reaction, generating polyethylene glycol dichloroacetate, further using the polyethylene glycol dichloroacetate to carry out oxygen alkylation reaction with a phenolic compound, and finally obtaining the polyethylene glycol aryloxyacetate. The preliminary biological activity test proves that as the series of the compounds integrate two active units of aryloxyacetic acid and the polyethylene glycol and have the superposition effect of activators, the compounds have obvious promotion role for rooting and sprouting of rapeseeds at a certain concentration, thereby being a type of novel plant growth regulators with high activity, low toxicity and good environmental compatibility.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to a kind of compound of biologically active---polyethylene glycol aryloxyacetate and preparation method thereof; The invention still further relates to of the application of this polyethylene glycol aryloxyacetate as plant-growth regulator.
Background technology
China is a large agricultural country that has a large population and a few land, and the output that improves the unit cultivated area is to solve one of food problem important measures, and the use of agricultural chemicals can not be ignored the contribution that improves per unit area yield.Agricultural chemicals is the chemical substance that a class has the particular organisms active function, and it not only can avoid the harm of various harmful organisms to farm crop, and can promote the growth of crop, improves the anti-pessimum energy of crop, improves the quality of crop.Plant-growth regulator is an important component part of modern agricultural chemicals, and people can utilize it to regulate and control the growth of crop.
Aryloxyacetic acid and derivative thereof, as ester, acid amides, hydrazides, quaternary ammonium salt and an alkali metal salt etc. are because its cheap, easy preparation is the widely used plant-growth regulator of a class.They all have the intensive physiologically active to growth and development of plant, and trace imposes on the farm crop and can grow by stimulating plant, and production-increasing function is remarkable.For example 4-chlorophenoxyacetic acid is 10
-6～10
-5In the concentration range, growth and development of plant there is promoter action, can prevents fallen flowers, increase fruit-setting rate, shorten the fructescence, improve the taste of fruits and vegetables, and prolong its fresh keeping time; When its concentration increases to 0.2%, will influence the metabolism of plant, cell growth inhibiting and tissue differentiation are so be used as the weedkiller of broadleaf weeds in the Gramineae cereal again.
Polyoxyethylene glycol (PEG) is handled crop seed, seed germination and impermeabilisation coerced etc. have promoter action, the salt tolerance and the seed vitality of seed have been promoted, can improve rate of emergence and seedling vigor, this to early emerge, cultivate strong sprout, prolong the plant strain growth phase, to increase output significant, so polyoxyethylene glycol to cause be to produce the method that goes up the raising seed vitality of using always.Because its good solubility energy, and molecular weight ranges is very wide, nontoxic, can be after utilizing polyoxyethylene glycol that multiple bioactive compounds is modified according to the combinatorial chemistry principle to seek new plant growth regulator more alternative is provided.
Summary of the invention
The compound that the purpose of this invention is to provide a series of biologically actives---polyethylene glycol aryloxyacetate.
Another object of the present invention provides a kind of preparation method of polyethylene glycol aryloxyacetate.
A further object of the invention just provides the application of a kind of polyethylene glycol aryloxyacetate in crop growth.
(1) polyethylene glycol aryloxyacetate
The structural formula of polyethylene glycol aryloxyacetate of the present invention is as follows
Wherein, R=4-CH
3CONH, 4-Cl, 2-Cl-4-Cl, 2-CH
3, 3-NO
2, 4-CH
3Or 3-CH
3
(2) preparation of polyethylene glycol aryloxyacetate
The preparation method of polyethylene glycol aryloxyacetate of the present invention is to generate the two chloracetates of polyoxyethylene glycol with chloroacetyl chloride and polyoxyethylene glycol reaction earlier, reacts through o-alkylation with two chloracetates of polyoxyethylene glycol and phenolic compound again, obtains polyethylene glycol aryloxyacetate.Its concrete processing step is as follows:
1, the two chloracetates of intermediate polyoxyethylene glycol is synthetic
With the methylene dichloride is solvent, is acid binding agent with the triethylamine, and polyoxyethylene glycol and chloroacetyl chloride are with 1: 3～1: 4 mol ratio, in stirring at room reaction 24～30 hours, with 1～5%NaHCO
3Solution washing is removed the intact chloroacetyl chloride of unreacted, separates, and organic phase is extremely approaching neutral with the saturated common salt water washing, anhydrous Na
2SO
4Drying is filtered, and steaming desolventizes, and after products therefrom is dissolved with methylene dichloride, again with the anhydrous diethyl ether precipitation, obtains the two chloracetates of polyoxyethylene glycol.
The concrete operations step is: earlier polyoxyethylene glycol is dissolved in the methylene dichloride, adds triethylamine, behind the thorough mixing, system is cooled to 0～5 ℃, (concentration is 1.062～1.416mol/L) slowly to add the dichloromethane solution of chloroacetyl chloride again; Slowly be warming up to stirring at room reaction 24～30 hours; With mass concentration 1～5%NaHCO
3Solution washing is removed the intact chloroacetyl chloride of unreacted, separates, and organic phase is extremely approaching neutral with the saturated common salt water washing, anhydrous Na
2SO
4Drying is filtered, and steaming desolventizes, and after products therefrom is dissolved with methylene dichloride, again with the anhydrous diethyl ether precipitation, obtains the two chloracetates of polyoxyethylene glycol.
Described polyoxyethylene glycol is poly(oxyethylene glycol) 400～6000, preferred Polyethylene Glycol-600.
Mole such as the consumption of described acid binding agent triethylamine and chloroacetyl chloride.
2, polyethylene glycol aryloxyacetate is synthetic
Mixing solutions with acetone, acetonitrile or acetone and toluene is a solvent, K
2CO
3Make alkali, KI makes catalyzer, two chloracetates of polyoxyethylene glycol and phenolic compound were with 1: 2.5～1: 3 mol ratio, in 50～60 ℃ of back flow reaction 30～36h, cooling, cross the filtering inorganic salt, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～3: 1 column chromatography separate or with ether repeatedly wash product.
The concrete operations step is: earlier with phenolic compound, K
2CO
3Be dissolved in the above-mentioned solvent,, phenol be converted into phenol sylvite in 30～60 ℃ of back flow reaction 2～4h; The two chloracetates of polyoxyethylene glycol, KI are dissolved in the above-mentioned solvent,, make it be converted into the iodo macrogol ester, add aforementioned phenolic compound and K more gradually in normal-temperature reaction 2～4h
2CO
3Solution in, in 50～60 ℃ of stirring and refluxing reaction, 30～36h; The filtering inorganic salt are crossed in cooling, and steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1 or with ether repeatedly wash product.
Described phenolic compound is acamol, para-chlorophenol, 2,4 dichloro phenol, ortho-methyl phenol, m-nitrophenol, p-methyl phenol or m-methyl phenol.
The mixing solutions that alkylated reaction solvent of the present invention is acetone, acetonitrile or acetone and toluene (volume ratio of acetone and toluene is 1: 1～1: 1.5).But when making solvent with acetonitrile, though productive rate is higher, because price is more expensive, and toxic; And acetone is cheap and easy to get, and boiling point is lower, and aftertreatment is removed easily, so as the choice solvent of alkylated reaction.
The synthetic route of polyethylene glycol aryloxyacetate of the present invention is shown below:
Wherein, R=4-CH
3CONH, 4-Cl, 2-Cl-4-Cl, 2-CH
3, 3-NO
2, 4-CH
3Or 3-CH
3
(3) spectral data analysis
In the ir data of polyethylene glycol aryloxyacetate, all products are all at 1750cm
-1Near strong absorption peak has appearred, correspond to the stretching vibration of ester carbonyl group; In addition, 2900cm
-1Near CH appears
2The stretching vibration of middle c h bond, 1100cm
-1Neighbouring is aliphatic ether C-O-C absorption peak, and 1249cm
-1Near be aromatic oxide C-O-C absorption peak, illustrate that Polyethylene Glycol-600 pair chloracetates (PEG-600DCA) have carried out the o-alkylation reaction with different phenol.
1In the H NMR spectrum, be the example explanation with 2a, δ 2.19 is the hydrogen on the fragrant methyl, δ 8.42 be (resonance absorbing peak CONH-), δ 6.84～7.54 is the resonance absorbing peak of (ArH), δ 4.63 is (ArOCH
2-) resonance absorbing peak, δ 4.35～4.39th, (COOCH
2-ofPEG) resonance absorbing peak, δ 3.56～3.74th, (OCH
2CH
2O-of PEG) resonance absorbing peak, Spectrum Analysis is consistent with the structure of target compound.
(4) biological activity test
Adopt plate culture, this series compound is made into the solution of six concentration of 100～0.001mg/L respectively, study its growth regulating effect to the rape seedlings root, do blank test with distilled water, the indolylacetic acid solution of same concentrations is done standard control, the length of room temperature growth and measurement rape root, calculate the active per-cent of adjusting with following formula:
A＝(N-N
0)/N
0×100％
A---for sample is regulated active
N---in compound solution, cultivate the length of the root that records
N
0---in distilled water, cultivate the root length that records
The polyethylene glycol aryloxyacetate of the present invention's preparation sees Table 1 to the data of plant growth regulating activity.
Table 1 plant growth regulating activity data
Above-mentioned biological activity test shows:
1, along with the reduction of concentration shows certain gradation law to the growth regulating-activity of root.Majority of compounds is when high density 100mg/L, growth to crop all shows restraining effect, and 1,0.1,0.01, under three concentration of 0.001mg/L, polyethylene glycol aryloxyacetate (2a, 2b, 2c, 2f, 2g) has promoter action to the rape growth of seedlings, and all is better than indolylacetic acid.
2, in above-mentioned seven kinds of compounds, 2b (polyoxyethylene glycol p-chlorophenoxyacetic acid ester) is when concentration 0.01mg/L, and best to the promoter action of rape seedling, the promotion rate is 386%.
3, the position in different functional groups and the functional group compound of living in all can exert an influence to the biological activity of compound, and the present position is that an ortho position replacement＜para-orientation＜position replaces to the bioactive enhanced activity of compound for same functional group.
4, owing to the wetting ability of polyoxyethylene glycol, this series compound is all selected pure water in process for preparation be solvent, reduced the pollution to environment, nontoxic, environmental protection.
In sum, the polyethylene glycol aryloxyacetate of the present invention's preparation is owing to have both aryloxyacetic acid, two kinds of activity units of polyoxyethylene glycol, has active sub synergetic effect, and preliminary biological activity test shows, the new plant growth regulator that this series compound to the obvious facilitation that rooted of Semen Brassicae campestris, is the active height of a class when the concentration of 1～0.001mg/L, toxicity is low, Environmental compatibility is good.
Embodiment
The present invention is described further below by concrete experiment.
Embodiment 1: compound 2a's (polyoxyethylene glycol acetparaminosalol phenoxy acetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
PEG600 (3.54mmol) with 2.124g, the distilled triethylamine of the methylene dichloride of 20mL and 2mL (14.16mmol) joins in the two neck flasks of 50mL, and thorough mixing is cooled to system 0～5 ℃ then, slowly drip the dichloromethane solution (1.6g of chloroacetyl chloride, 14.16mmol chloroacetyl chloride is dissolved in the methylene dichloride of 10mL), dropwised in about one hour, slowly be warming up to room temperature after, continued stirring reaction 24 hours, stopped reaction slowly adds water, and uses mass concentration 5%NaHCO
3Washing makes unreacted chloroacetyl chloride hydrolysis; Be transferred to separating funnel, shake up, leave standstill the back layering, layer oily matter repeatedly washs with saturated common salt again, until approaching neutral.Solution adds anhydrous Na
2SO
4Drying is filtered, and steaming desolventizes, and after at last products therefrom being dissolved with methylene dichloride, with anhydrous diethyl ether precipitation at least twice, obtains the two chloracetates of Polyethylene Glycol-600, productive rate about 85%.
(2) compound 2a's is synthetic
With acamol 1a (7.5mmol), K
2CO
3(7.5mmol) be dissolved in the 15ml acetone, in 60 ℃ of back flow reaction 3h; PEG600DCA (2.5mmol) and KI (4mmol) are dissolved in the 10ml acetone, and normal-temperature reaction 3h adds aforementioned acamol 1a, K gradually
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2a is as follows:
The relevant physico-chemical property of compound 2a, spectroscopy data are distinguished as follows:
2a: yellow oily, productive rate 74.7%; IR (KBr), v/cm
-1: 1754 (COO), 1250 (aryl oxide COC), 1100 (fat ether COC), 2913,2859 (CH
2), 3064 (NH);
1H NMR (CDCl
3, 400MHz) δ: 2.19 (s, 6H, CH
3), 8.42 (s, 2H, NH), 6.84～7.54 (m, 8H, ArH), 4.63 (s, 4H, ArOCH
2), 4.35～4.39 (m, 4H ,-COOCH
2-of PEG), 3.56～3.74 (m ,-OCH
2CH
2O-ofPEG).
Embodiment 2: compound 2b's (polyoxyethylene glycol p-chlorophenoxyacetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
With embodiment 1.
(2) compound 2b's is synthetic
With para-chlorophenol 1b (7.5mmol), K
2CO
3(7.5mmol) be dissolved in 15ml acetone, 60 ℃ of back flow reaction 3h; PEG600DCA (2.5mmol) and KI (4mmol) are dissolved in the 10ml acetone, in normal-temperature reaction 3h; Add aforementioned para-chlorophenol 1b, K then gradually
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2b is as follows:
The relevant physico-chemical property of compound 2b, spectroscopy data are distinguished as follows:
2b: yellow oily, productive rate 81.2%; IR (KBr), v/cm
-1: 1753 (COO), 1249 (aryl oxide COC), 1099 (fat ether COC), 2923,2857 (CH
2);
1H NMR (CDCl
3, 400MHz) δ: 6.80～7.19 (m, 8H, ArH), 4.62 (s, 4H, ArOCH
2), 4.33～4.39 (m, 4H ,-COOCH
2-of PEG), 3.58-3.70 (m ,-OCH
2CH
2O-of PEG).
Embodiment 3: compound 2c's (polyoxyethylene glycol 2,4 dichlorophenoxyacetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
With embodiment 1.
(2) compound 2c's is synthetic
With 2,4 dichloro phenol 1c (7.5mmol), K
2CO
3(7.5mmol) be dissolved in the 15ml acetone, in 60 ℃ of back flow reaction 3h; PEG600DCA (2.5mmol) and KI (4mmol) are dissolved in the 10ml acetone,, add aforementioned chlorophenesic acid 1c, K then gradually in normal-temperature reaction 3h
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2c is as follows:
The relevant physico-chemical property of compound 2c, spectroscopy data are distinguished as follows:
2c: yellowish brown mucus shape, productive rate 76.4%; IR (KBr), v/cm
-1: 1755 (COO), 1249 (aryl oxide COC), 1096 (fat ether COC), 2914,2857 (CH
2);
1H NMR (CDCl
3, 400MHz) δ: 7.01～7.39 (m, 6H, ArH), 4.77 (s, 4H, ArOCH
2), 4.39～4.41 (m, 4H ,-COOCH
2-ofPEG), 3.61～3.80 (m ,-OCH
2CH
2O-of PEG).
Embodiment 4: compound 2d's (polyoxyethylene glycol o-methyl-benzene fluoroacetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
With embodiment 1.
(2) compound 2d's is synthetic
With ortho-methyl phenol 1d (7.5mmol), K
2CO
3(7.5mmol) be dissolved in the 15ml acetone, in 60 ℃ of back flow reaction 3h; PEG600DCA (2.5mmol) and KI (4mmol) are dissolved in the 10ml acetone,, join aforementioned ortho-methyl phenol 1d, K then gradually in normal-temperature reaction 3h
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2d is as follows:
The relevant physico-chemical property of compound 2c, spectroscopy data are distinguished as follows:
The relevant physico-chemical property of compound 2d, spectroscopy data are distinguished as follows:
2d: yellowish brown mucus shape, productive rate 70.4%; IR (KBr), v/cm
-1: 1756 (COO), 1250 (aryl oxide COC), 1108 (fat ether COC), 2873,2873 (CH
2);
1H NMR (CDCl
3, 400MHz) δ: 2.18 (s, 6H, CH
3), 6.70～7.18 (m, 8H, ArH), 4.69 (s, 4H, ArOCH
2), 4.33～4.38 (m, 4H ,-COOCH
2-of PEG), 3.63～3.77 (m ,-OCH
2CH
2O-of PEG).
Embodiment 5: compound 2e's (polyoxyethylene glycol m-nitro fluoroacetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
With embodiment 1.
(2) compound 2e's is synthetic
With m-nitrophenol 1e (7.5mmol), K
2CO
3(7.5mmol) be dissolved in the 15ml acetone,, PEG600DCA (2.5mmol) and KI (4mmol) be dissolved in the 10ml acetone,, join aforementioned m-nitrophenol 1e, K then gradually in normal-temperature reaction 3h in 60 ℃ of back flow reaction 3h
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2e is as follows:
The relevant physico-chemical property of compound 2e, spectroscopy data are distinguished as follows:
2e: yellowish brown mucus shape, productive rate 79.8%; IR (KBr), v/cm
-1: 1754 (COO), 1250 (aryl oxide COC), 1105 (fat ether COC), 2903,2873 (CH
2);
1H NMR (CDCl
3, 400MHz) δ: 7.28～7.83 (m, 8H, ArH), 4.80 (s, 4H, ArOCH
2), 4.33～4.39 (m, 4H ,-COOCH
2-ofPEG), 3.66～3.79 (m ,-OCH
2CH
2O-of PEG).
Embodiment 6: compound 2f's (polyoxyethylene glycol is to the methyl phenoxy acetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
With embodiment 1.
(2) compound 2f's is synthetic
With p-methyl phenol 1f (7.5mmol), K
2CO
3(7.5mmol) be dissolved in the 15ml acetone, in 60 ℃ of back flow reaction 3h; PEG600DCA (2.5mmol) and KI (4mmol) are dissolved in the 10ml acetone, in normal-temperature reaction 3h; Join aforementioned p-methyl phenol 1f, K then gradually
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2f is as follows:
2f: brown mucus shape, productive rate 73.8%; IR (KBr), v/cm
-1: 1755 (COO), 1250 (aryl oxide COC), 1106 (fat ether COC), 2897,2875 (CH
2);
1H NMR (CDCl
3, 400MHz) δ: 2.18 (s, 6H, CH
3), 6.80～7.10 (m, 8H, ArH), 4.65 (s, 4H, ArOCH
2), 4.33～4.40 (m, 4H ,-COOCH
2-of PEG), 3.56～3.74 (m ,-OCH
2CH
2O-of PEG).
Embodiment 7: compound 2g's (polyoxyethylene glycol m-methyl phenoxyacetic acid ester) is synthetic
(1) two chloracetate (PEG-600DCA) intermediates of Polyethylene Glycol-600 is synthetic
With embodiment 1.
(2) compound 2g's is synthetic
With m-methyl phenol 1g (7.5mmol), K
2CO
3(7.5mmol) be dissolved in the 15ml acetone, in 60 ℃ of back flow reaction 3h; PEG600DCA (2.5mmol) and KI (4mmol) are dissolved in the 10ml acetone,, add aforementioned m-methyl phenol 1g, K gradually in normal-temperature reaction 3h
2CO
3Acetone soln in, in 60 ℃ of backflow stirring reaction 36h, stopped reaction, the filtering inorganic salt are crossed in cooling, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1, or with ether repeatedly wash product.
The synthetic route of 2g is as follows:
The relevant physico-chemical property of compound 2g, spectroscopy data are distinguished as follows:
2g: brown mucus shape, productive rate 77.7%; IR (KBr), v/cm
-1: 1754 (COO), 1250 (aryl oxide COC), 1105 (fat ether COC), 2898,2873 (CH
2);
1H NMR (CDCl
3, 400MHz) δ: 2.18 (s, 6H, CH
3), 6.71～7.20 (m, 8H, ArH), 4.66 (s, 4H, ArOCH
2), 4.33～4.40 (m, 4H ,-COOCH
2-of PEG), 3.61～3.79 (m ,-OCH
2CH
2O-of PEG).
Claims (10)
1. polyethylene glycol aryloxyacetate, its structure is as follows:
Wherein, R=4-CH
3CONH, 4-Cl, 2-Cl-4-Cl, 2-CH
3, 3-NO
2, 4-CH
3Or 3-CH
3
2. the preparation method of polyethylene glycol aryloxyacetate according to claim 1, be to generate the two chloracetates of polyoxyethylene glycol with chloroacetyl chloride and polyoxyethylene glycol reaction earlier, react through o-alkylation with two chloracetates of polyoxyethylene glycol and phenolic compound again, obtain polyethylene glycol aryloxyacetate.
3. as the preparation method of polyethylene glycol aryloxyacetate as described in the claim 2, it is characterized in that: the technology that described chloroacetyl chloride and polyoxyethylene glycol reaction generate the two chloracetates of polyoxyethylene glycol is: be solvent with the methylene dichloride, with the triethylamine is acid binding agent, polyoxyethylene glycol and chloroacetyl chloride were with 1: 3～1: 4 mol ratio, in stirring at room reaction 24～30 hours, use NaHCO
3Solution washing is removed the intact chloroacetyl chloride of unreacted, separates, and organic phase is extremely approaching neutral with the saturated common salt water washing, anhydrous Na
2SO
4Drying is filtered, and steaming desolventizes, and after products therefrom dissolves with methylene dichloride, again with the anhydrous diethyl ether precipitation, obtains the two chloracetates of polyoxyethylene glycol;
Described polyoxyethylene glycol is poly(oxyethylene glycol) 400～6000;
Mole such as the consumption of described acid binding agent triethylamine and chloroacetyl chloride;
Described NaHCO
3The mass concentration of solution is 1～5%.
4. as the preparation method of polyethylene glycol aryloxyacetate as described in the claim 3, it is characterized in that: the technology that described chloroacetyl chloride and polyoxyethylene glycol reaction generate the two chloracetates of polyoxyethylene glycol is: earlier polyoxyethylene glycol is dissolved in the methylene dichloride, add the acid binding agent triethylamine, behind the thorough mixing, system is cooled to 0～5 ℃, slowly adds the dichloromethane solution of chloroacetyl chloride again; Slowly be warming up to room temperature, stirring reaction 24～30 hours; Use NaHCO then
3Solution washing is removed the intact chloroacetyl chloride of unreacted, separates, and organic phase is extremely approaching neutral with the saturated common salt water washing, anhydrous Na
2SO
4Drying is filtered, and steaming desolventizes, and after products therefrom is dissolved with methylene dichloride, again with the anhydrous diethyl ether precipitation, obtains the two chloracetates of polyoxyethylene glycol.
5. as the preparation method of polyethylene glycol aryloxyacetate as described in the claim 4, it is characterized in that: the dichloromethane solution concentration of described chloroacetyl chloride is 1.062～1.416mol/L.
6. as the preparation method of polyethylene glycol aryloxyacetate as described in the claim 2, it is characterized in that: the technology that two chloracetates of described polyoxyethylene glycol and phenolic compound reaction generate polyethylene glycol aryloxyacetate is: the mixing solutions with acetone, acetonitrile or acetone and toluene is a solvent, with K
2CO
3Make alkali, KI makes catalyzer, two chloracetates of polyoxyethylene glycol and phenolic compound were with 1: 2.5～1: 3 mol ratio, in 50～60 ℃ of back flow reaction 30～36h, cooling, remove by filter inorganic salt, steaming desolventizes, with crude product acetone: sherwood oil=1: 1～3: 1 column chromatography separate or with ether wash product;
Described K
2CO
3Consumption be 1.0～1.5 times of phenolic compound molar weight;
The consumption of catalyzer KI is 0.5～1.5 times of the two chloracetate molar weights of polyoxyethylene glycol.
7. as the preparation method of polyethylene glycol aryloxyacetate as described in the claim 6, it is characterized in that: earlier with phenolic compound and K
2CO
3Be dissolved in the described solvent, in 30～60 ℃ of back flow reaction 2～4h; Again the two chloracetates of polyoxyethylene glycol, KI are dissolved in the described solvent,, add phenolic compound and K then gradually in normal-temperature reaction 2～4h
2CO
3Solution in, in 50～60 ℃ of stirring and refluxing reaction, 30～36h; Cooling removes by filter inorganic salt, and steaming desolventizes, with crude product acetone: sherwood oil=1: 1～column chromatography separation in 3: 1 or with ether wash product.
8. as the preparation method of polyethylene glycol aryloxyacetate as described in the claim 2,6,7, it is characterized in that: described phenolic compound is acamol, para-chlorophenol, 2,4 dichloro phenol, ortho-methyl phenol, m-nitrophenol, p-methyl phenol or m-methyl phenol.
According to claim 1 polyethylene glycol aryloxyacetate as the application of plant-growth regulator.
10. polyethylene glycol aryloxyacetate is characterized in that as the application of plant-growth regulator according to claim 1: the polyethylene glycol aryloxyacetate water is mixed with the solution that concentration is 1～0.001mg/L.
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| US9492444B2 (en) | 2013-12-17 | 2016-11-15 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded extended release abuse deterrent pill |
| US9707184B2 (en) | 2014-07-17 | 2017-07-18 | Pharmaceutical Manufacturing Research Services, Inc. | Immediate release abuse deterrent liquid fill dosage form |
| US10172797B2 (en) | 2013-12-17 | 2019-01-08 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded extended release abuse deterrent pill |
| US10195153B2 (en) | 2013-08-12 | 2019-02-05 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded immediate release abuse deterrent pill |
| US10959958B2 (en) | 2014-10-20 | 2021-03-30 | Pharmaceutical Manufacturing Research Services, Inc. | Extended release abuse deterrent liquid fill dosage form |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10195153B2 (en) | 2013-08-12 | 2019-02-05 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded immediate release abuse deterrent pill |
| US10639281B2 (en) | 2013-08-12 | 2020-05-05 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded immediate release abuse deterrent pill |
| US9492444B2 (en) | 2013-12-17 | 2016-11-15 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded extended release abuse deterrent pill |
| US10172797B2 (en) | 2013-12-17 | 2019-01-08 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded extended release abuse deterrent pill |
| US10792254B2 (en) | 2013-12-17 | 2020-10-06 | Pharmaceutical Manufacturing Research Services, Inc. | Extruded extended release abuse deterrent pill |
| US9707184B2 (en) | 2014-07-17 | 2017-07-18 | Pharmaceutical Manufacturing Research Services, Inc. | Immediate release abuse deterrent liquid fill dosage form |
| US10959958B2 (en) | 2014-10-20 | 2021-03-30 | Pharmaceutical Manufacturing Research Services, Inc. | Extended release abuse deterrent liquid fill dosage form |
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