CN101537395A - Synthetic method of floating agent of organophosphorous compound and organophosphorous floating agent - Google Patents
Synthetic method of floating agent of organophosphorous compound and organophosphorous floating agent Download PDFInfo
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- 238000007667 floating Methods 0.000 title claims abstract description 23
- 150000002903 organophosphorus compounds Chemical class 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 73
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims abstract description 73
- 150000002466 imines Chemical class 0.000 claims abstract description 72
- 229940061584 phosphoramidic acid Drugs 0.000 claims abstract description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 32
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 29
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 28
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 96
- 150000001875 compounds Chemical class 0.000 claims description 87
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 59
- 238000002360 preparation method Methods 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000003480 eluent Substances 0.000 claims description 42
- 238000012856 packing Methods 0.000 claims description 42
- 239000000741 silica gel Substances 0.000 claims description 42
- 229910002027 silica gel Inorganic materials 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 27
- 238000010025 steaming Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 21
- 238000010408 sweeping Methods 0.000 claims description 21
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 20
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 17
- 230000006837 decompression Effects 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 14
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 11
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- KTPQDAFAZUCXSP-UHFFFAOYSA-N ethanol;propan-1-amine Chemical compound CCO.CCCN KTPQDAFAZUCXSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 18
- 239000011707 mineral Substances 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract 2
- 238000004440 column chromatography Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- 238000005303 weighing Methods 0.000 description 19
- 230000002194 synthesizing effect Effects 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000008396 flotation agent Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 10
- 238000005188 flotation Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 238000005065 mining Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 201000007094 prostatitis Diseases 0.000 description 1
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- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
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Abstract
The invention discloses a synthetic method of a floating agent of organophosphorous compound and the organophosphorous floating agent, belonging to the technical field of mineral separation. The synthetic method comprises the steps of: taking phosphorus trichloride as a phosphorus source, dissolving parahydroxyben-zaldehyde in ethanol, slowly dropping excess propylamine, reacting at room temperature, then obtaining product imine, using the mixture of the phosphorus trichloride and petroleum ether to prepare phosphite ester in a mixing liquid of the ethanol and the petroleum ether, then using the phosphite ester, the imine and anhydrous ether to prepare the mixture of phosphoramidic acid, imine, small amount of phosphite ester and solvent ether, and then conducting distillation, column chromatography and separation to obtain the organophosphorous floating agent phosphoramidic acid, therefore the method obtains 20 types of phosphoramidic acid compounds, and from which, 2-3 efficient and novel organophosphorous floating agents can be selected for use. The invention has simple synthetic method, easy operation and short period, and the obtained organophosphorous floating agent is widely applied to mineral dressing due to special structure thereof.
Description
Technical field
The invention belongs to the mineral separation technology field, particularly a kind of synthetic method of organic phosphorus compound floating agent phosphoramidic acid.
Background technology
Flotation is a kind of important method during mineral separate, and is widely used in fields such as mining industry, medicine, environmental protection.It is utilize mineral surfaces hydrophobic-hydrophilic difference and mineral between surface wettability difference, adopt artificial mode of adding flotation agent to separate.It is that Brokenshidre is invented before about 100 years than the logical company in lining-BHP Billiton.At present, flotation has become a kind of main method for separating that all need adopt in mining industry and other a lot of industrial departments.
Low-grade ore is meant under the condition of technology and economy of mining design, because the major constituent grade is lower, the ore of economic loss appears in exploitation separately.Under traditional two index systems, it mainly shows as unbalanced-ore and ultra-poor ore deposit.
China is resource big country, and the mineral resources gross reserves occupies prostatitis, the world, but resource distribution is extremely unbalanced, and mineral resources belong to the mineral products of complicated, difficult choosing, low-grade, many metals symbiosis mostly, has caused great difficulty for the development and utilization of mineral products.
The utilization in low-grade multi-metal complex ore deposit, China mine has the enormous quantity potentiality.According to the introduction of the mid-90 in 20th century Liu's literary talent, in 53 emphasis iron ores of China, there are 21 mines to have a large amount of unbalanced-ores, add up 7.21 hundred million tons more than, its quantity is considerable, if add the ultra-poor ore deposit that might utilize, its quantity is more huge.In nonferrous mine, also have a large amount of low-grade ores, as the large-scale copper mine of China, its between 0.1%～0.3% low-grade ore just reach 5.27 hundred million tons.Along with the progress of technique of preparing, metal recovery rate improves constantly, and the space of mine Low Grade Ore Utilization will increase day by day.
In low-grade multi-metal complex ore deposit, character is very approaching because some mineral swims, and mineral embedding cloth is superfine, complex structure, and oxidation is serious, and clay content is many etc., causes and recycles difficulty.And along with the continuous exploitation utilization of mineral resources, it is more and more poorer that limited mineral resources become, and mineral resources constantly develop to poor, thin, assorted, difficult characteristics, use conventional method and ore-dressing technique to be difficult to obtain sorting index preferably.In order to solve this difficult problem, at the concrete condition of ore, vast ore dressing scientific worker develops and has developed many new methods.Wherein, flotation is good with its selectivity, handles the particulate difficulty and selects low-grade ore than other beneficiation method efficient height, and the concentration ratio advantages of higher more and more is subject to the people's attention.
The medicament that uses in the floatation process is called flotation agent.Flotation agent plays a crucial role in floatation process, and the quality of flotation effect largely depends on the quality of floating agent.So searching and the efficient flotation agent of development of new become the main key of development flotation technology.Floating agent commonly used comprises collecting agent, foaming agent, adjustment agent etc., in order to increase or to reduce the hydrophobicity of mineral surfaces, adjusts, controls the flotation behavior of mineral chemistry condition and mineral, to obtain separating resulting preferably.By the annual quantity survey (surveying) of producing coal, metallic ore and nonmetallic ore in the whole world, the annual floating agent worth up to multi-million dollar that consumes in the whole world.
In numerous flotation agent, organophosphor flotation agent obtains extensive studies with its special construction and uses in ore dressing, can be illustrated this from three aspects:
The organic phosphorus compound chain close atom number can be adjusted in a big way.
2. the sterically hindered and electronic effect adjustable extent that causes of organic phosphorus compound nonpolar group is big.
3. among the particularity ≡ PO of bonded atom or the ≡ PS Multiple Bonds but not two key.
The particularity of this three aspect makes organic phosphorus compound as flotation agent, seems more promising than other types compound.
In research and application before, often only pay attention to the effect of simple function group, the compound of polyfunctional group effect is studied seldom.And seek the floating agent of specified performance in the past, mainly be by virtue of experience and carry out screening test.Traditional medicine of looking for by rule of thumb, because the work purpose is poor, the lead time is long, and workload is big, and success rate is low, far can not satisfy the demand.The development of structure of matter theory provides new method for this reason, promptly by the relation of structure and performance, looks for medicine.Generally be referred to as " MOLECULE DESIGN ".At present, both at home and abroad seldom to the research of flotation agent MOLECULE DESIGN.Therefore, to the design of flotation agent molecule, particularly, become very urgent to the research of the organophosphor floating agent MOLECULE DESIGN of polyfunctional group effect.
Summary of the invention
The objective of the invention is at the characteristics in low-grade multi-metal oxygen ore deposit and a kind of synthetic method and organophosphor flotation agent of floating agent of organic phosphorus compound are provided, it is characterized in that, described synthetic a series of organic phosphorus compounds (phosphoramidic acid), the general formula of these compounds:
Alkyl R wherein
1, R
2, R
3Can be designed to a series of group.
The a series of organic compounds that contain phenyl ring do not contain a series of organic compounds of phenyl ring
Be some organic compounds that I synthesize during this period of time below:
1. a series of organic compounds that contain phenyl ring: (8 kinds)
2. a series of organic compounds that do not contain phenyl ring: (12 kinds)
The synthetic method of the floating agent of described organic phosphorus compound comprises the steps:
1) with the phosphorus trichloride is the phosphorus source, ethanol n-propylamine, parahydroxyben-zaldehyde
2) preparation of imines: parahydroxyben-zaldehyde, benzaldehyde or hutanal are dissolved in ethanol, n-butanol, sec-butyl alcohol or the isopropyl alcohol, slowly drip excessive n-propylamine, isopropylamine, tert-butylamine or n-octyl amine, room temperature condition is reaction down, and behind the stirring reaction, decompression distillation obtains product imine;
3) preparation of phosphite ester: will in ice bath, stir behind ethanol and the benzinum mixing, slowly drip phosphorus trichloride PCl then
3With the mixture of benzinum in ethanol and benzinum mixed liquor, drip off back 40 ℃ and refluxed 2 hours, last decompression distillation steams solvent, obtains the product phosphite ester;
4) preparation of phosphoramidic acid: the little magneton of in three mouthfuls of round-bottomed flasks, packing into, add absolute ether, get and seal after phosphite ester that step 2 obtains is poured flask into, in ice bath, stir behind the mixing, drop into the imines that step 1 obtains again, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days,
5) revolve steaming, the material that obtains after the above-mentioned reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether, revolve steam solvent after, what obtain is the mixture of three kinds of compounds;
6) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product;
7) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into;
8) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2;
9) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors;
10) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid;
11) collect the 3rd point, revolve steaming and obtain the product phosphoramidic acid.
The invention has the beneficial effects as follows that synthetic method is simple, easy to operate, the cycle is short, and gained organophosphor flotation agent is widely used in ore dressing with its special construction.
The specific embodiment
The present invention is directed to the characteristics in low-grade multi-metal oxygen ore deposit and a kind of synthetic method and organophosphor flotation agent of floating agent of organic phosphorus compound are provided.The floating agent of described organic phosphorus compound comprises that a series of organic compounds that contain phenyl ring do not contain a series of organic compounds of phenyl ring, the general formula of these compounds:
Alkyl R wherein
1, R
2, R
3Can be designed to a series of group.
The synthetic method of the floating agent of described organic phosphorus compound comprises the steps:
1) with the phosphorus trichloride is the phosphorus source, ethanol n-propylamine, parahydroxyben-zaldehyde
2) preparation of imines: parahydroxyben-zaldehyde, benzaldehyde or hutanal are dissolved in ethanol, n-butanol, sec-butyl alcohol or the isopropyl alcohol, slowly drip excessive n-propylamine, isopropylamine, tert-butylamine or n-octyl amine, room temperature condition is reaction down, and behind the stirring reaction, decompression distillation obtains product imine;
3) preparation of phosphite ester: will in ice bath, stir behind ethanol and the benzinum mixing, slowly drip phosphorus trichloride PCl then
3With the mixture of benzinum in ethanol and benzinum mixed liquor, drip off back 40 ℃ and refluxed 2 hours, last decompression distillation steams solvent, obtains the product phosphite ester;
4) preparation of phosphoramidic acid: the little magneton of in three mouthfuls of round-bottomed flasks, packing into, add absolute ether, get and seal after phosphite ester that step 2 obtains is poured flask into, in ice bath, stir behind the mixing, drop into the imines that step 1 obtains again, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days,
5) revolve steaming, the material that obtains after the above-mentioned reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether, revolve steam solvent after, what obtain is the mixture of three kinds of compounds;
6) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product;
7) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into;
8) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2;
9) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors;
10) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid;
11) collect the 3rd point, revolve steaming and obtain the product phosphoramidic acid.
Come the numerical value and the proportionate relationship of each parameter in the concrete above-mentioned steps below by the building-up process of 20 kinds of compounds and result.
First kind of compound: experimental raw: ethanol, phosphorus trichloride, n-propylamine, parahydroxyben-zaldehyde.
Experimentation:
1) preparation of imines: 6.1 gram parahydroxyben-zaldehydes are dissolved in the 15ml absolute ethyl alcohol, slowly drip 8.2ml (excessive) n-propylamine, room temperature condition reaction down, stirring reaction is after 3 hours, and decompression distillation obtains product 8.05 grams.Productive rate 98.77%
2) preparation of phosphite ester: in ice bath, stir after measuring 20ml absolute ethyl alcohol and 20ml benzinum (boiling range is 30 ℃～60 ℃) mixing, slowly drip 8.8mlPCl
3With the mixture of 10ml benzinum, drip off back 40 ℃ and refluxed 2 hours.Last decompression distillation steams solvent, obtains product 12.15 grams, productive rate 88%
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 1.591 gram phosphite esters, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.879 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 2.161 grams.Productive rate 62.4%.
Second kind of compound: experimental raw: ethanol, phosphorus trichloride, isopropylamine, parahydroxyben-zaldehyde.
Experimentation:
1) preparation of imines: 6.1 gram parahydroxyben-zaldehydes are dissolved in the 15ml absolute ethyl alcohol, slowly drip 10ml (excessive) isopropylamine, room temperature condition reaction down, stirring reaction is after 3 hours, and decompression distillation obtains product 7.985 grams, productive rate 96%
2) preparation of phosphite ester: prepared when synthesizing first kind of compound.
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 0.69 gram phosphite ester, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.371 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 0.722 gram.Productive rate 48%.
The third compound: experimental raw: ethanol, phosphorus trichloride, n-propylamine, benzaldehyde.
Experimentation:
1) preparation of imines: measure the 6.06ml benzaldehyde, add the 5ml absolute ethyl alcohol and make solvent, slowly drip 10ml (excessive) n-propylamine, room temperature condition reaction down, stirring reaction is after 3 hours, and decompression distillation obtains product 7.884 grams.Productive rate 90%
2) preparation of phosphite ester: prepared when synthesizing first kind of compound.
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.
Take by weighing 1.38 gram phosphite esters, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.47 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 2.07 grams.Productive rate 73%.Product is a white solid.
The 4th kind of compound: experimental raw: ethanol, phosphorus trichloride, isopropylamine, benzaldehyde.
Experimentation:
1) preparation of imines: measure the 6.06ml benzaldehyde, add the 5ml absolute ethyl alcohol and make solvent, slowly drip 10ml (excessive) isopropylamine, room temperature condition reaction down, stirring reaction is after 3 hours, and decompression distillation obtains product 7.786 grams.Productive rate 98%
2) preparation of phosphite ester: prepared when synthesizing first kind of compound.
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 0.69 gram phosphite ester, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.47 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 0.805 gram.Productive rate 56%.
The 5th kind of compound: experimental raw: ethanol, phosphorus trichloride, tert-butylamine, parahydroxyben-zaldehyde.
Experimentation:
1) preparation of imines: take by weighing the 6.1g parahydroxyben-zaldehyde, add the 15ml absolute ethyl alcohol and make solvent, slowly drip 10ml (excessive) tert-butylamine, room temperature condition reaction down, stirring reaction is after 3 hours, and decompression distillation obtains product 7.842 grams.Productive rate 93%
2) preparation of phosphite ester: prepared when synthesizing first kind of compound.
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 0.69 gram phosphite ester, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.50 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 0.704 gram.Productive rate 45%.
The 6th kind of compound: experimental raw: ethanol, phosphorus trichloride, tert-butylamine, benzaldehyde.
Experimentation:
1) preparation of imines: measure the 6.06ml benzaldehyde, add the 5ml absolute ethyl alcohol and make solvent, slowly drip 10ml (excessive) tert-butylamine, room temperature condition reaction down, stirring reaction is after 3 hours, and decompression distillation obtains product 7.326 grams.Productive rate 91%
2) preparation of phosphite ester: prepared when synthesizing first kind of compound.
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 0.69 gram phosphite ester, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.01 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 0.448 gram.Productive rate 30%.
The 7th kind of compound: experimental raw: isopropyl alcohol, phosphorus trichloride, isopropylamine, benzaldehyde.
Experimentation:
1) preparation of imines: prepared when synthesizing the 4th kind of compound.
2) preparation of phosphite ester: in ice bath, stir after measuring 12ml isopropyl alcohol and 15ml benzinum (boiling range is 30 ℃～60 ℃) mixing, slowly drip 4.4mlPCl
3With the mixture of 10ml benzinum, drip off back 40 ℃ and refluxed 2 hours.Last decompression distillation steams solvent, obtains product 4.88 grams, productive rate 88%
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 0.849 gram phosphite ester, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 0.961 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 0.543 gram.Productive rate 34%.
The 8th kind of compound: experimental raw: isopropyl alcohol, phosphorus trichloride, isopropylamine, parahydroxyben-zaldehyde.
Experimentation:
1) preparation of imines: prepared when synthesizing second kind of compound.
2) preparation of phosphite ester: prepared when synthesizing the 7th kind of compound.
3) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 24ml absolute ether.Take by weighing 1.66 gram phosphite esters, seal after pouring flask into.Stir in ice bath behind the mixing, drop into 1.80 gram imines, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
4) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
5) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
6) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into.
7) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2
8) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
9) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
10) collect the 3rd point, revolve steaming and obtain product 0.643 gram.Productive rate 20%.
Below 12 kinds of compounds owing to very easily do not decompose with the imines of phenyl ring, synthesizing imine is synthetic does not separately come out.So adopt one kettle way to prepare phosphoramidic acid.
The 9th kind of compound: experimental raw: ethanol, phosphorus trichloride, n-propylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing first kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 6.48 gram phosphite esters, measure the 4.125ml n-propylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 4.455ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.973 grams.Productive rate 20%.
The tenth kind of compound: experimental raw: ethanol, phosphorus trichloride, isopropylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing first kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 3.76 gram phosphite esters, measure the 2.6ml isopropylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.6ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.717 grams.Productive rate 24%.
The 11 kind of compound: experimental raw: n-butanol, phosphorus trichloride, n-propylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: in ice bath, stir after measuring 41.12ml n-butanol and 40ml benzinum (boiling range is 30 ℃～60 ℃) mixing, slowly drip 13.2mlPCl
3With the mixture of 15ml benzinum, drip off back 40 ℃ and refluxed 2 hours.Last decompression distillation steams solvent, obtains product 25.55 grams, productive rate 88%
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 5.85 gram phosphite esters, measure the 3.0ml n-propylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.68ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.278 grams.Productive rate 14%.
The 12 kind of compound: experimental raw: ethanol, phosphorus trichloride, tert-butylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing the 11 kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 3.728 gram phosphite esters, measure the 3.5ml tert-butylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.6ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.345 grams.Productive rate 19%.
The 13 kind of compound: experimental raw: isopropyl alcohol, phosphorus trichloride, n-propylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing the 7th kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 6.30 gram phosphite esters, measure the 4.125ml n-propylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 4.455ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.043 grams.Productive rate 14%.
The 14 kind of compound: experimental raw: sec-butyl alcohol, phosphorus trichloride, n-propylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: in ice bath, stir after measuring 41.26ml sec-butyl alcohol and 40ml benzinum (boiling range is 30 ℃～60 ℃) mixing, slowly drip 13.2mlPCl
3With the mixture of 15ml benzinum, drip off back 40 ℃ and refluxed 2 hours.Last decompression distillation steams solvent, obtains product 25.6 grams, productive rate 88%
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 5.88 gram phosphite esters, measure the 3.0ml n-propylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.7ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.432 grams.Productive rate 15%.
The 15 kind of compound: experimental raw: n-butanol, phosphorus trichloride, n-octyl amine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing the 11 kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 4.82 gram phosphite esters, measure the 5.0ml n-octyl amine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.7ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 8
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming and obtain product 1.377 grams.Productive rate 14%.
Below several may be solvent ratio not choosing also have a certain amount of phosphite ester not remove causing product not separated fully as can be seen from the nuclear magnetic spectrogram the inside.So these are several to be mixtures of phosphoramidic acid and phosphite ester, carry out at present about this part work that separates.
The 16 kind of compound: experimental raw: n-butanol, phosphorus trichloride, isopropylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing the 11 kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 5.85 gram phosphite esters, measure the 3.0ml isopropylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.7ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming.
The 17 kind of compound: experimental raw: sec-butyl alcohol, phosphorus trichloride, isopropylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing the 14 kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 5.88 gram phosphite esters, measure the 3.0ml isopropylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 2.7ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming.
The 18 kind of compound: experimental raw: isopropyl alcohol, phosphorus trichloride, isopropylamine, hutanal.
Experimentation:
1) preparation of phosphite ester: prepared when synthesizing the 7th kind of compound.
2) the little magneton of packing in three of the preparation of phosphoramidic acid: 100ml mouthfuls of round-bottomed flasks adds the 20ml anhydrous methylene chloride.Take by weighing 5.82 gram phosphite esters, measure the 4.125ml isopropylamine, seal after pouring flask into.In ice bath, stir behind the mixing, slowly drip the 4.455ml hutanal, drip the recession deicing and bathe.Adopt oil bath to add hot reflux, temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days.
3) material that obtains after the reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has methylene chloride.Revolve steam solvent after, what obtain is the mixture of three kinds of compounds.
4) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product.
5) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 200ml silica gel of packing into.
6) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 4
7) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors.
8) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid.
9) collect the 3rd point, revolve steaming.
Two kinds of compounds to be synthesized:
(n-octyl amine and tert-butylamine belong to illegal drug after May Day, reagent company stops to sell, and can't buy on the market) for want of raw materials.
The 19 kind of compound: experimental raw: sec-butyl alcohol, phosphorus trichloride, n-octyl amine, hutanal.
The 20 kind of compound: experimental raw: isopropyl alcohol, phosphorus trichloride, tert-butylamine, hutanal.
The organophosphor flotation agent that can filter out 2～3 new high-efficiencies from above-mentioned 20 kinds of compounds uses.
Claims (2)
1. the floating agent of an organic phosphorus compound is characterized in that, what the floating agent of described organic phosphorus compound comprised 8 kinds of serial organic compounds that contain phenyl ring and do not contain phenyl ring shows 12 kinds of organic compounds; The general formula of these compounds is:
Alkyl R wherein
1, R
2, R
3Can be designed to a series of group.
2. the synthetic method of the floating agent of a described organic phosphorus compound is characterized in that, the synthetic method of the floating agent of described organic phosphorus compound comprises the steps:
1) with the phosphorus trichloride is the phosphorus source, ethanol n-propylamine, parahydroxyben-zaldehyde
2) preparation of imines: parahydroxyben-zaldehyde, benzaldehyde or hutanal are dissolved in ethanol, n-butanol, sec-butyl alcohol or the isopropyl alcohol, slowly drip excessive n-propylamine, isopropylamine, tert-butylamine or n-octyl amine, room temperature condition is reaction down, and behind the stirring reaction, decompression distillation obtains product imine;
3) preparation of phosphite ester: will in ice bath, stir behind ethanol and the benzinum mixing, slowly drip phosphorus trichloride PCl then
3With the mixture of benzinum in ethanol and benzinum mixed liquor, drip off back 40 ℃ and refluxed 2 hours, last decompression distillation steams solvent, obtains the product phosphite ester;
4) preparation of phosphoramidic acid: the little magneton of in three mouthfuls of round-bottomed flasks, packing into, add absolute ether, get and seal after phosphite ester that step 2 obtains is poured flask into, in ice bath, stir behind the mixing, drop into the imines that step 1 obtains again, reaction temperature is controlled at 40 ℃～50 ℃.Reaction time is 3 days,
5) revolve steaming, the material that obtains after the above-mentioned reaction is product phosphoramidic acid and imines and a spot of phosphite ester, also has solvent ether, revolve steam solvent after, what obtain is the mixture of three kinds of compounds;
6) cross post: owing to what obtain is the mixture of three kinds of compounds, must separate product from mixture, adopts the method for post to isolate product;
7) dress pillar: the blade diameter length ratio of pillar is 1: 15, adopts benzinum to make eluant, eluent, the 100ml silica gel of packing into;
8) some plate (TLC) is determined the solvent ratio: should determine through TLC less than 0.3 because climb the Rf value of plate, adopt solvent ratio benzinum: ethyl acetate=1: 2;
9) install and begin to go up sample behind the pillar, will guarantee during last sample to want even on the sample, and can not get excited the layer of silica gel of the superiors;
10) gone up behind the sample beginning and dashed a little while with eluant, eluent earlier, and then added solvent and began pillar, being swept away what come earlier is imines, secondly is phosphite ester, and sweeping away what come at last is phosphoramidic acid;
11) collect the 3rd point, revolve steaming and obtain the product phosphoramidic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910135675A CN101537395A (en) | 2008-12-04 | 2009-04-24 | Synthetic method of floating agent of organophosphorous compound and organophosphorous floating agent |
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| CN200910135675A CN101537395A (en) | 2008-12-04 | 2009-04-24 | Synthetic method of floating agent of organophosphorous compound and organophosphorous floating agent |
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| CN101537395A true CN101537395A (en) | 2009-09-23 |
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| CN103951701A (en) * | 2014-04-15 | 2014-07-30 | 中南大学 | Amino phosphonic acid compound as well as preparation and application methods thereof |
| CN105149107A (en) * | 2015-07-13 | 2015-12-16 | 中南大学 | Application of phosphoric acid ester compound to flotation of calcium-containing minerals |
| CN106674274A (en) * | 2016-02-29 | 2017-05-17 | 中蓝连海设计研究院 | Phosphate mineral inhibitor as well as preparation method and use thereof |
| CN107225048A (en) * | 2017-07-01 | 2017-10-03 | 山东金城柯瑞化学有限公司 | Coal flotation agent |
| CN110201801A (en) * | 2019-06-18 | 2019-09-06 | 武汉工程大学 | A kind of hydroxyethylidene diphosphonic acid stearate soap collecting agent and preparation method thereof |
| CN111482278A (en) * | 2020-06-03 | 2020-08-04 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN112808463A (en) * | 2020-12-30 | 2021-05-18 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
| CN112973968A (en) * | 2021-02-04 | 2021-06-18 | 中南大学 | Flotation reagent and flotation separation method for pyrite-chalcopyrite |
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- 2009-04-24 CN CN200910135675A patent/CN101537395A/en active Pending
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| CN103951701B (en) * | 2014-04-15 | 2015-12-09 | 中南大学 | A kind of aminophosphonic acid compounds and methods for making and using same thereof |
| CN103951701A (en) * | 2014-04-15 | 2014-07-30 | 中南大学 | Amino phosphonic acid compound as well as preparation and application methods thereof |
| CN105149107A (en) * | 2015-07-13 | 2015-12-16 | 中南大学 | Application of phosphoric acid ester compound to flotation of calcium-containing minerals |
| CN106674274B (en) * | 2016-02-29 | 2019-04-26 | 中蓝连海设计研究院有限公司 | A kind of phosphate mineral inhibitor and preparation method thereof and purposes |
| CN106674274A (en) * | 2016-02-29 | 2017-05-17 | 中蓝连海设计研究院 | Phosphate mineral inhibitor as well as preparation method and use thereof |
| CN107225048B (en) * | 2017-07-01 | 2019-07-12 | 山东金城柯瑞化学有限公司 | Coal flotation agent |
| CN107225048A (en) * | 2017-07-01 | 2017-10-03 | 山东金城柯瑞化学有限公司 | Coal flotation agent |
| CN110201801A (en) * | 2019-06-18 | 2019-09-06 | 武汉工程大学 | A kind of hydroxyethylidene diphosphonic acid stearate soap collecting agent and preparation method thereof |
| CN111482278A (en) * | 2020-06-03 | 2020-08-04 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN111482278B (en) * | 2020-06-03 | 2022-03-22 | 广东省资源综合利用研究所 | Copper oxide ore flotation method |
| CN112808463A (en) * | 2020-12-30 | 2021-05-18 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
| CN112808463B (en) * | 2020-12-30 | 2022-06-21 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
| CN112973968A (en) * | 2021-02-04 | 2021-06-18 | 中南大学 | Flotation reagent and flotation separation method for pyrite-chalcopyrite |
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