CN1775723A - Bromo-2, 4'-dihydroxy diphenyl ether compound and its synthesizing method - Google Patents
Bromo-2, 4'-dihydroxy diphenyl ether compound and its synthesizing method Download PDFInfo
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- CN1775723A CN1775723A CN 200510022125 CN200510022125A CN1775723A CN 1775723 A CN1775723 A CN 1775723A CN 200510022125 CN200510022125 CN 200510022125 CN 200510022125 A CN200510022125 A CN 200510022125A CN 1775723 A CN1775723 A CN 1775723A
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Abstract
The inventiona relates to bromo-2, 4'-dihydroxyl diphenyl ether compound and its synthesizing method, using 2-methoxy phenol and 4-methoxy chlorobenzene as raw materials, and it is an antimicrobial obtained by three-step reaction, and has better antimicrobial activity to Escherichia coli, catarrh diplococcus, Staphylococcus aureus, Staphylococcus Albus, bacillus proteus, etc. and avoids producing highly toxic dioxin compound in the producing and using course, avoiding environmental pollution and damaging human health; and also overcomes the shortages that natural bromic2, 4'-dihydroxyl diphenyl ether antimicrobial can form highly toxic dioxin compound in use on certain conditions, and the natural bromic2, 4'-dihydroxyl diphenyl ether antimicrobial has limited source, complex extracting course and high cost.
Description
Invention field
The present invention relates to halogenated diphenyl ether antiseptic-germicide compounds and synthetic method thereof.
Background of invention
The halogenated hydroxyl phenyl ether is important sterilant of a class and antiseptic-germicide, compound 1 triclosan (2 wherein, 4,4 '-three chloro-2 '-dihydroxy diphenyl ether) as broad spectrum antimicrobicide gram-positive microorganism, Gram-negative bacteria, fungi and virus are had very strong inhibition and kill activity, be widely applied to industries such as daily use chemicals, weaving, building materials and plastics.
Compound 1
Triclosan itself is to the human body safety non-toxic, but the production of triclosan is extensively adopted with 2 in the world at present, 4-chlorophenesic acid, 2,5 dichloronitrobenzenes are raw material, technology through condensation, reduction, diazotization, hydrolysis and operations such as separating, in this technology, make and very easily carry high toxicity impurity, polychlorinated dibenzo compound 2, dioxin-like compounds 3 in the product.
Compound 2 compounds 3
1969 by Sharma etc. at Tetrahedron Lett (1969,17,1715) proposed from a class ocean cavernous body, to extract since the dihydroxy diphenyl ether of bromo 2-more than the three kinds compounds 4,5,6 on first, the foreign scholar has carried out a large amount of research work of this compounds, find that they have good biological activity, can suppress gram-positive microorganism and negative bacterium effectively.
Compound 4 compounds 5 compounds 6
Brad in 1981 etc. Tetrahedron (1981,37,2335) go up to propose from the ocean cavernous body of another kind of Dysides, to isolate bromo 2,2 more than two kinds '-dihydroxy diphenyl ether compound 7,8, they all have better antibacterial activity.
Compound 7 compounds 8
Nineteen ninety-five Xiong etc. J.Nat.Prod (1995,58,1384) go up to propose from the ocean cavernous body of Dysides, to isolate bromo 2,2 more than four kinds '-dihydroxy diphenyl ether compound 7,8,9,10, find that they also have better antibacterial activity.
Compound 9 compounds 10
Calendar year 2001 Natalia etc. are at J.Nat.Prod (2001,64,151) also mention in, they are except isolating compound 7,8 from the ocean cavernous body of Dysides, also isolate two Zhong dioxin-like compounds 11,12, these natural many bromos 2,2 that also give to separate, purify '-dihydroxy diphenyl ether brought difficulty.
Compound 11 compounds 12
Control compounds 7,8 and 11,12 as can be seen, when generating natural product Dysides, except generating natural many bromos 2,2 '-dihydroxy diphenyl ether outside, natural many bromos 2,2 '-dihydroxy diphenyl ether is the same with triclosan under certain condition intramolecular substitution reaction has also taken place have been generated and has stable six-membered ring structure De dioxin-like compound.
In sum, though natural bromo 2,2 '-dihydroxy diphenyl ether has better antibacterial activity, isolated bromo 2,2 '-dihydroxy diphenyl ether is owing to have bromine atoms, hydroxyl simultaneously at the ehter bond ortho position, may generate dioxin-like compound under certain condition; And natural many bromos 2,2 '-the dihydroxy diphenyl ether source is limited, the leaching process complexity, and cost is higher, thereby makes the widespread use of this type of antiseptic-germicide be restricted.
Goal of the invention
The present invention designs and synthesizes bromo 2,4 '-the dihydroxy diphenyl ether antiseptic-germicide, this type of bromo 2,4 '-the dihydroxy diphenyl ether antiseptic-germicide do not contain bromine atoms, hydroxyl simultaneously at the ehter bond ortho position, in synthetic and use, can not form highly toxic dioxin-like compound, and carry out anti-microbial activity research at multiple harmful bacterium,, low toxicity efficient, novel diphenyl ether antiseptic-germicide to filter out.
Summary of the invention
Target compound of the present invention be bromo 2,4 '-dihydroxy diphenyl ether compound, its constitutional features is 2 and 4 ' that two hydroxyls lay respectively at the different phenyl ring of phenyl ether, the structure of target compound is:
TM3 TM4
The present invention prepare bromo 2,4 '-synthetic method of dihydroxy diphenyl ether antiseptic-germicide is:
The first step 2,4 '-preparation of dimethoxy phenyl ether:
In the 500mL three-necked bottle, add K respectively
2CO
3, CuCl, pyridine, 2-methoxyphenol, 4-methoxyl group chlorobenzene, its mol ratio is 1～1.1: 0.045～0.45: 0.05～0.1: 1～1.1: 1, under magnetic agitation, heat, temperature was reacted 15～20 hours down for 150～200 ℃, and TLC detection reaction terminal point is after having reacted, use ethyl acetate extraction, with the washing of 5%NaOH dilute solution, washing, dry, steaming desolventizes, and gets the white solid crude product, crude product sherwood oil recrystallization, drying, the productive rate 40.0～50.0% of product;
Second step 2,4 '-preparation of dihydroxy diphenyl ether:
In the three-necked bottle of 250mL, add 2 respectively, 4 '-dimethoxy phenyl ether, Hydrogen bromide, glacial acetic acid, its mol ratio is 1: 2～5: 50～60, is heated to backflow, 110～130 ℃ of reflux temperatures, TLC detection reaction terminal point, after having reacted, glacial acetic acid is removed in decompression, gets the white solid crude product, crude product sherwood oil recrystallization, product yield 85.0～90.0%;
The 3rd step bromo 2,4 '-preparation of dihydroxy diphenyl ether:
In the 100mL three-necked bottle, add 2,4 '-dihydroxy diphenyl ether, methylene dichloride, ethyl acetate, its mol ratio is 1: 20～40: 12.5～25, be heated to backflow, 50～65 ℃ of reflux temperatures are with liquid bromine, methylene dichloride, ethyl acetate, its mol ratio is 1～4.25: 20～40: 12.5～25 mixing solutions splashes in the three-necked bottle, TLC detection reaction terminal point reacts to redness and takes off substantially, with 3%～5%Na
2S
2O
3Solution washing is removed unreacted bromine, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product gets bromination product with the sherwood oil recrystallization, the productive rate 70.0%～80.0% of product.
The invention effect
1. synthetic method the present invention adopts 4 bromos 2 with new texture that synthetic method obtains, 4 '-the dihydroxy diphenyl ether antiseptic-germicide, overcome natural bromo 2,2 '-the dihydroxy diphenyl ether antiseptic-germicide may form highly toxic dioxin-like compound under certain condition; Also overcome natural bromo 2,2 '-dihydroxy diphenyl ether antiseptic-germicide source is limited, leaching process is complicated, cost is higher deficiency.
2. antibacterial tests is carried out anti-microbial activity test back discovery to target compound of the present invention, they possess better antibacterial activity to intestinal bacteria, catalin diplococcus, streptococcus aureus, Staphylococcus albus, Candida albicans, Bacillus proteus, Pseudomonas solanacearum, and the anti-microbial activity of some bacterial classification is higher than broad spectrum antimicrobicide triclosan (Triclosan).The target compound anti-microbial activity the results are shown in following table.
(data are antibacterial circle diameter to table target compound anti-microbial activity result, unit: millimeter)
| A | B | C | D | E | F | G | |
| Sterilized water | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| Dehydrated alcohol | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| Triclosan | 25 | 23 | 23 | 20 | 22 | 21 | 19 |
| TM1 | 22 | 21 | 22 | 18 | 22 | 17 | 17 |
| TM2 | 24 | 23 | 21 | 19 | 22 | 15 | 22 |
| TM3 | 22 | 22 | 21 | 17 | 20 | 19 | 17 |
| TM4 | 25 | 22 | 22 | 18 | 21 | 19 | 18 |
Sample: TM1 5-bromo-2,4 '-dihydroxy diphenyl ether; TM2 5,3 '-two bromo-2,4 '-dihydroxy diphenyl ether; TM35,3 ', 5 '-three bromo-2,4 '-dihydroxy diphenyl ether; TM4 3,5,3 ', 5 '-tetrabromobisphenol, 4 '-dihydroxy diphenyl ether
Bacterial classification: A, Candida albicans B, Staphylococcus albus C, streptococcus aureus D, Bacillus proteus E, intestinal bacteria F, Pseudomonas solanacearum G, OK a karaoke club diplococcus
Experimental technique: sample thief 0.1 gram is dissolved in 10 milliliters of ethanol, dilutes 100 times, gets in 0.1 milliliter of Oxford cup on the flat board that scribbles each bacterial classification of diluent, cultivates observations after 40 hours for 37 ℃.
The present invention will be described in further detail with the following Examples:
Embodiment 1:2,4 '-preparation of dimethoxy phenyl ether
(1) has magnetic stirring apparatus one, add 0.2mol K in the three-necked bottle of thermometer and reflux condensing tube
2CO
3, 0.009mol CuCl, 0.1mol pyridine, 0.22mol 2-methoxyphenol and 0.2mol 4-methoxyl group chlorobenzene, at 200 ℃ of reactions 20 hours down, TLC detection reaction terminal point, after having reacted, with ethyl acetate extraction (20mL * 3 time), with 5%NaOH dilute solution washing (3 times), washing (3 times), dry, steaming desolventizes, and gets the white solid crude product, crude product sherwood oil 50mL recrystallization, drying, product yield 46.0%.
(2) have magnetic stirring apparatus one, add 0.2mol K in the three-necked bottle of thermometer and reflux condensing tube
2CO
3, 0.009mol CuCl, 0.1mol pyridine, 0.22mol 2-methoxyphenol and 0.2mol 4-methoxyl group chlorobenzene, at 150 ℃ of reactions 15 hours down, TLC detection reaction terminal point, after having reacted, with ethyl acetate extraction (20mL * 3 time), with 5%NaOH dilute solution washing (3 times), washing (3 times), dry, steaming desolventizes, and gets the white solid crude product, crude product sherwood oil 50mL recrystallization, drying, product yield 48.0%.
Embodiment 2:2,4 '-preparation of dihydroxy diphenyl ether
(1) has magnetic stirring apparatus one, add 0.05mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dimethoxy phenyl ether, 0.25mol Hydrogen bromide and 3.0mol glacial acetic acid, reflux, TLC detection reaction terminal point, after having reacted, glacial acetic acid is removed in decompression, crude product sherwood oil 60mL recrystallization, product yield 90.0%.
(2) have magnetic stirring apparatus one, add 0.05mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dimethoxy phenyl ether, 0.2mol Hydrogen bromide and 3.0mol glacial acetic acid, reflux, TLC detection reaction terminal point, after having reacted, glacial acetic acid is removed in decompression, crude product sherwood oil 60mL recrystallization, product yield 88.0%.
Embodiment 3:5-bromo-2,4 '-preparation of dihydroxy diphenyl ether
(1) has magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), the 0.004mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (methylene dichloride: ethyl acetate=15: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 10mL 3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (methylene dichloride: ethyl acetate=20: 1, V: V) obtain target compound, productive rate 75.0% through column chromatography;
1HNMR (CDCl
3, 400MHz): 4.843 (s, 1H, OH), 5.659 (s, 1H, OH), 6.835 (d, J=2.4Hz, 1H, ArH), 6.841 (dd, J=8.8Hz, 2H, ArH), 6.886 (d, J=8.4Hz, 1H, ArH), 6.936 (dd, J=8.8Hz, 2H, ArH), 7.067 (dd, J=8.8Hz, 2.4Hz, 1H, ArH); IR (KBr) v:3288,1430,900,818,777cm
-1MSm/z (%): 281 (M+, 100).
(2) have magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), the 0.0041mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (methylene dichloride: ethyl acetate=15: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 10mL3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (methylene dichloride: ethyl acetate=20: 1, V: V) obtain target compound, productive rate 77.0% through column chromatography.
Embodiment 4:5,3 '-two bromo-2,4 '-preparation of dihydroxy diphenyl ether
(1) has magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), the 0.008mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (methylene dichloride: ethyl acetate=50: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 10mL 3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (sherwood oil: methylene dichloride=1: 1, V: V) obtain target compound, productive rate 78.0% through column chromatography;
1HNMR (CDCl
3, 400MHz): 5.429 (s, 1H, OH), 5.575 (s, 1H, OH), 6.869 (d, J=2.0Hz, 1H, ArH), 6.901 (d, J=8.8Hz, 1H, ArH), 6.944 (dd, J=8.8Hz, 2.8Hz, 1H, ArH), 7.030 (d, J=8.8Hz, 1H, ArH), 7.109 (dd, J=8.4Hz, 2.4Hz, 1H, ArH), 7.191 (d, J=2.4Hz, 1H, ArH); IR (KBr) v:3266,1598,1196,924,812cm
-1MS m/z (%): 360 (M
+, 100).
(2) have magnetic stirring apparatus one, add O.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, ethyl acetate O.045mol, after the reflux (60 ℃ of reflux temperatures), the 0.0081mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (methylene dichloride: ethyl acetate=50: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 1OmL3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (sherwood oil: methylene dichloride=1: 1, V: V) obtain target compound, productive rate 80.0% through column chromatography.
Embodiment 5:5,3 ', 5 '-three bromo-2,4 '-preparation of dihydroxy diphenyl ether
(1) has magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), the 0.012mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (sherwood oil: methylene dichloride=1: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 1OmL3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (sherwood oil: methylene dichloride=2: 1, V: V) obtain target compound, productive rate 78.0% through column chromatography;
1HNMR (CDCl
3, 400MHz): 5.552 (s, 1H, OH), 5.778 (s, 1H, OH), 6.910 (d, J=2.4Hz, 1H, ArH), 6.916 (d, J=8.8Hz, 1H, ArH), 7.151 (dd, J=8.8Hz, 2.4Hz, 1H, ArH), 7.197 (s, 2H, ArH); IR (KBr) v:3420,1590,1208,938,858,786cm
-1MSm/z (%): 439 (M
+, 100).
(2) have magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), the 0.0121mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (sherwood oil: methylene dichloride=1: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 10mL3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (sherwood oil: methylene dichloride=2: 1, V: V) obtain target compound, productive rate 79.0% through column chromatography.
Embodiment 6:3,5,3 ', 5 '-tetrabromobisphenol, 4 '-preparation of dihydroxy diphenyl ether
(1) has magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), O.016mol bromine is dissolved in methylene dichloride O.080mol and the mixing solutions formed of ethyl acetate O.045mol, slowly splash in the three-necked bottle, with TLC monitoring reaction process (sherwood oil: methylene dichloride=2: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 1OmL 3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (sherwood oil: methylene dichloride=4: 1, V: V) obtain target compound, productive rate 74.0% through column chromatography;
1HNMR (CDCl
3, 400MHz): 5.774 (s, 1H, OH), 5.791 (s, 1H, OH), 6.893 (d, J=2.OHz, 1H, ArH), 7.175 (s, 2H, ArH), 7.421 (d, J=2.4Hz, 1H, ArH); IR (KBr) v:3420,1588,1194,956,844,788,700cm
-1MSm/z (%): 518 (M
+, 100).
(2) have magnetic stirring apparatus one, add 0.004mol 2 in the three-necked bottle of thermometer and reflux condensing tube, 4 '-dihydroxy diphenyl ether, 0.080mol methylene dichloride, 0.045mol ethyl acetate, after the reflux (60 ℃ of reflux temperatures), the 0.0161mol bromine is dissolved in the mixing solutions of 0.080mol methylene dichloride and 0.045mol ethyl acetate composition, slowly splash in the three-necked bottle, with TLC monitoring reaction process (sherwood oil: methylene dichloride=2: 1, V: V), reaction is finished, be chilled to room temperature, with the Na of 1OmL 3%
2S
2O
3Solution washing three times is washed three times again, tells organic layer, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product separates (sherwood oil: methylene dichloride=4: 1, V: V) obtain target compound, productive rate 78.0% through column chromatography.
Claims (2)
- Bromo 2,4 '-dihydroxy diphenyl ether compound and synthetic method thereof, the constitutional features of its target compound is 2 and 4 ' that two hydroxyls lay respectively at the different phenyl ring of phenyl ether, its concrete structure is as follows:
- 2. synthetic method for preparing this diphenyl ether compound shown in claim 1 is characterized in that:The first step 2,4 '-preparation of dimethoxy phenyl ether:In the 500mL three-necked bottle, add K respectively 2CO 3, CuCl, pyridine, 2-methoxyphenol, 4-methoxyl group chlorobenzene, its mol ratio is 1～1.1: 0.045～0.45: 0.05～0.1: 1～1.1: 1, under magnetic agitation, heat, temperature was reacted 15～20 hours down for 150～200 ℃, and TLC detection reaction terminal point is after having reacted, use ethyl acetate extraction, with the washing of 5%NaOH dilute solution, washing, dry, steaming desolventizes, and gets the white solid crude product, crude product sherwood oil recrystallization, drying, the productive rate 40.0～50.0% of product;Second step 2,4 '-preparation of dihydroxy diphenyl ether:In the three-necked bottle of 250mL, add 2 respectively, 4 '-dimethoxy phenyl ether, Hydrogen bromide, glacial acetic acid, its mol ratio is 1: 2～5: 50～60, is heated to backflow, 110～130 ℃ of reflux temperatures, TLC detection reaction terminal point, after having reacted, glacial acetic acid is removed in decompression, gets the white solid crude product, crude product sherwood oil recrystallization, product yield 85.0～90.0%; The 3rd step bromo 2,4 '-preparation of dihydroxy diphenyl ether:In the 100mL three-necked bottle, add 2,4 '-dihydroxy diphenyl ether, methylene dichloride, ethyl acetate, its mol ratio is 1: 20～40: 12.5～25, be heated to backflow, 50～65 ℃ of reflux temperatures are with liquid bromine, methylene dichloride, ethyl acetate, its mol ratio is 1～4.25: 20～40: 12.5～25 mixing solutions splashes in the three-necked bottle, TLC detection reaction terminal point reacts to redness and takes off substantially, with 3%～5%Na 2S 2O 3Solution washing is removed unreacted bromine, drying, and steaming desolventizes, and gets the light yellow solid crude product, and crude product gets bromination product with the sherwood oil recrystallization, the productive rate 70.0%～80.0% of product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015032218A1 (en) * | 2013-09-07 | 2015-03-12 | 宁波市雨辰环保科技有限公司 | Application of bisphenol salt in preparing disinfectant used for sterilization or for formaldehyde removal |
| CN107827716A (en) * | 2017-09-28 | 2018-03-23 | 大连天源基化学有限公司 | The residual processing method of kettle in the production of 1 (4 phenoxy phenoxy base) 2 propyl alcohol |
| CN115028518A (en) * | 2022-06-30 | 2022-09-09 | 南方海洋科学与工程广东省实验室(广州) | Preparation and application of 2,2' -oxo-bis-1, 4-di-tert-butylbenzene |
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Cited By (3)
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|---|---|---|---|---|
| WO2015032218A1 (en) * | 2013-09-07 | 2015-03-12 | 宁波市雨辰环保科技有限公司 | Application of bisphenol salt in preparing disinfectant used for sterilization or for formaldehyde removal |
| CN107827716A (en) * | 2017-09-28 | 2018-03-23 | 大连天源基化学有限公司 | The residual processing method of kettle in the production of 1 (4 phenoxy phenoxy base) 2 propyl alcohol |
| CN115028518A (en) * | 2022-06-30 | 2022-09-09 | 南方海洋科学与工程广东省实验室(广州) | Preparation and application of 2,2' -oxo-bis-1, 4-di-tert-butylbenzene |
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