CN105906663A - Hydroxide radical benzylidene diphosphonic acid and preparation method thereof - Google Patents
Hydroxide radical benzylidene diphosphonic acid and preparation method thereof Download PDFInfo
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- CN105906663A CN105906663A CN201610390611.0A CN201610390611A CN105906663A CN 105906663 A CN105906663 A CN 105906663A CN 201610390611 A CN201610390611 A CN 201610390611A CN 105906663 A CN105906663 A CN 105906663A
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- CN
- China
- Prior art keywords
- described step
- phosphonic acid
- benzylidene
- ethylhexyl phosphonic
- diphosphonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000002360 preparation method Methods 0.000 title abstract description 9
- FRLTXWJJMCIUNT-UHFFFAOYSA-N ru78783 Chemical compound OP(O)(=O)C(P(O)(O)=O)C1=CC=CC=C1 FRLTXWJJMCIUNT-UHFFFAOYSA-N 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 33
- -1 hydroxyl benzal Chemical class 0.000 claims description 26
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 14
- 230000005494 condensation Effects 0.000 claims description 14
- 238000006482 condensation reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 229940122361 Bisphosphonate Drugs 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 0 *=P(C(c1ccccc1)(O)P(O)(O)=[U])(O)O Chemical compound *=P(C(c1ccccc1)(O)P(O)(O)=[U])(O)O 0.000 description 1
- ZCOMURCDMLBWOR-UHFFFAOYSA-N OC(c1ccccc1)(P(O)(O)=O)P(O)(O)=O Chemical compound OC(c1ccccc1)(P(O)(O)=O)P(O)(O)=O ZCOMURCDMLBWOR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3882—Arylalkanephosphonic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention belongs to the field of organic compound preparation methods, and particularly relates to hydroxide radical benzylidene diphosphonic acid and a preparation method thereof. The structural formula of the hydroxide radical benzylidene diphosphonic acid is shown in the description. The method comprises the steps that phosphorus acid and benzoyl chloride are adopted as raw materials, heating is performed under the normal pressure or micro-negative pressure state to generate crude hydroxide radical benzylidene diphosphonic acid, and then hydrolysis, suction filtration, drying and other working procedures are performed to obtain the finished hydroxide radical benzylidene diphosphonic acid. The preparation method has the advantages that the technological path is simple, operation is easy and convenient, the number of preparation facilities is small, and the three-waste discharge amount is small.
Description
Technical field
The invention belongs to organic compound preparation method field, especially relate to a kind of hydroxyl benzal di 2 ethylhexyl phosphonic acid and preparation thereof
Method.
Background technology
Hydroxyl benzal di 2 ethylhexyl phosphonic acid, faint yellow to white crystalline powder or flat crystal for one, it is mainly used as organic synthesis
And medicine intermediate, temporarily without traditional synthesis technique.
Summary of the invention
Based on this, the present invention provides a kind of hydroxyl benzal di 2 ethylhexyl phosphonic acid and preparation method thereof, and technique is simple, and by-product is few.
Technical solution of the present invention:
A kind of hydroxyl benzal di 2 ethylhexyl phosphonic acid, it is characterised in that: described hydroxyl benzal di 2 ethylhexyl phosphonic acid structural formula is as described below:
The method of the hydroxyl benzal di 2 ethylhexyl phosphonic acid described in making, said method comprising the steps of:
1) phosphorous acid and Benzenecarbonyl chloride. are joined in reaction bulb, open condensation reflux unit and agitating device, slowly
It is warmed up to condensation temp, and insulation carries out condensation reaction, obtains material 1；
2), after material 1 cooling, add water and be hydrolyzed reaction, obtain material 2；
3), after material 2 cooling, use buchner funnel sucking filtration, then gained filtering residue is transferred in vacuum drying oven decompression dry
Dry, obtain white crystal；
Complete the making of hydroxyl benzal di 2 ethylhexyl phosphonic acid.
Preferably, described step 1) the proportioning mol ratio of Benzenecarbonyl chloride. and phosphorous acid is 1:1～2.Directly with phosphorous acid,
Benzenecarbonyl chloride. and water are raw material, through benzoyl chemical combination and hydrolysis, react easily controllable, it is to avoid by-product
Generate, improve the yield of product.
Preferably, described step 1) condensation reaction pressure is normal pressure or tiny structure, described tiny structure parameter be 0～
10mmHg, setting-up point is 130～160 DEG C, and the response time is 5～8 hours, by Benzenecarbonyl chloride. and phosphorous
Acid is reacted, and obtains benzal diphosphonic acid crude product.React under the conditions of suitable tiny structure, make Benzenecarbonyl chloride. and phosphorous
Acid is fully reacted, and reduces the generation of byproduct of reaction.
Preferably, described step 2) to add the water yield be 2～3 times of material 1 mass.
Preferably, described step 2) material 1 is cooled to 40～60 DEG C, and add water hydrolysis, and hydrolysis temperature controls at 45～55 DEG C,
Hydrolysis time is 1～2 hour.
Preferably, described step 3) drying under reduced pressure condition is that, at 60～90 DEG C, under 600～750mmHg, decompression is dry
Dry 5～10 hours, use drying under reduced pressure, use drying under reduced pressure, it is possible to decrease baking temperature, improve rate of drying, separately
Can ensure that outward product property is stable, the purity of product and yield are high.
The technology of the present invention effect:
1, the present invention has the advantage that process route is simple, easy and simple to handle, it is few to prepare facility, " three wastes " discharge capacity is few；
2, the present invention is directly with phosphorous acid, Benzenecarbonyl chloride. and water as raw material, through benzoyl chemical combination and hydrolysis, instead
Should be easily controllable, it is to avoid the generation of by-product, improve the yield of product；
3, the present invention selects suitable condensation, hydrolysising condition, improves the yield of product, makes product yield reach 91%
Above.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Embodiment 1
A kind of hydroxyl benzal di 2 ethylhexyl phosphonic acid, it is characterised in that: described hydroxyl benzal di 2 ethylhexyl phosphonic acid structural formula is as described below:
Embodiment 2
The method of the hydroxyl benzal di 2 ethylhexyl phosphonic acid described in making, said method comprising the steps of:
1) phosphorous acid and Benzenecarbonyl chloride. are joined in reaction bulb, open condensation reflux unit and agitating device, slowly
It is warmed up to condensation temp, and insulation carries out condensation reaction, obtains material 1；
2), after material 1 cooling, add water and be hydrolyzed reaction, obtain material 2；
3), after material 2 cooling, use buchner funnel sucking filtration, then gained filtering residue is transferred in vacuum drying oven decompression dry
Dry, obtain white crystal；
Complete the making of hydroxyl benzal di 2 ethylhexyl phosphonic acid.
Described step 1) the proportioning mol ratio of Benzenecarbonyl chloride. and phosphorous acid is 1:1.
Described step 1) condensation reaction pressure is tiny structure, described tiny structure parameter is 10mmHg, condensation reaction temperature
Degree is 160 DEG C, and the response time is 5 hours.
Described step 2) to add the water yield be 2 times of material 1 mass.
Described step 2) material 1 is cooled to 40 DEG C, and add water hydrolysis, and hydrolysis temperature controls at 45 DEG C, hydrolysis
Time is 1 hour.
Described step 3) drying under reduced pressure condition is, at 60 DEG C, drying under reduced pressure 10 hours under 600mmHg.
The present embodiment hydroxyl benzal bisphosphonate product yield is 94.12%.
Embodiment 3
The method of the hydroxyl benzal di 2 ethylhexyl phosphonic acid described in making, said method comprising the steps of:
1) phosphorous acid and Benzenecarbonyl chloride. are joined in reaction bulb, open condensation reflux unit and agitating device, slowly
It is warmed up to condensation temp, and insulation carries out condensation reaction, obtains material 1；
2), after material 1 cooling, add water and be hydrolyzed reaction, obtain material 2；
3), after material 2 cooling, use buchner funnel sucking filtration, then gained filtering residue is transferred in vacuum drying oven decompression dry
Dry, obtain white crystal；
Complete the making of hydroxyl benzal di 2 ethylhexyl phosphonic acid.
Described step 1) the proportioning mol ratio of Benzenecarbonyl chloride. and phosphorous acid is 1:2.
Described step 1) condensation reaction pressure is tiny structure, described tiny structure parameter is 5mmHg, condensation reaction temperature
Degree is 130 DEG C, and the response time is 6 hours.
Described step 2) to add the water yield be 3 times of material 1 mass.
Described step 2) material 1 is cooled to 60 DEG C, and add water hydrolysis, and hydrolysis temperature controls at 55 DEG C, during hydrolysis
Between be 1 hour.
Described step 3) drying under reduced pressure condition is, at 90 DEG C, drying under reduced pressure 5 hours under 750mmHg.
The present embodiment hydroxyl benzal bisphosphonate product yield is 94.57%.
Embodiment 4
The method of the hydroxyl benzal di 2 ethylhexyl phosphonic acid described in making, said method comprising the steps of:
1) phosphorous acid and Benzenecarbonyl chloride. are joined in reaction bulb, open condensation reflux unit and agitating device, slowly
It is warmed up to condensation temp, and insulation carries out condensation reaction, obtains material 1；
2), after material 1 cooling, add water and be hydrolyzed reaction, obtain material 2；
3), after material 2 cooling, use buchner funnel sucking filtration, then gained filtering residue is transferred in vacuum drying oven decompression dry
Dry, obtain white crystal；
Complete the making of hydroxyl benzal di 2 ethylhexyl phosphonic acid.
Described step 1) the proportioning mol ratio of Benzenecarbonyl chloride. and phosphorous acid is 1:1.5.
Described step 1) condensation reaction pressure is tiny structure, described tiny structure parameter is 5mmHg, setting-up point
Being 150 DEG C, the response time is 7 hours.
Described step 2) to add the water yield be 2～3 times of material 1 mass.
Described step 2) material 1 is cooled to 50 DEG C, and add water hydrolysis, and hydrolysis temperature controls at 52 DEG C, hydrolysis
Time is 1.5 hours.
Described step 3) drying under reduced pressure condition is, at 70 DEG C, drying under reduced pressure 8 hours under 650mmHg.
The present embodiment hydroxyl benzal bisphosphonate product yield is 93.35%.
Embodiment 5
140.6g is added to the there-necked flask equipped with mechanical agitation, thermometer, spherical condensation tube (above connecing offgas duct)
Benzenecarbonyl chloride. (1.0mol) and 164.0g phosphorous acid (2.0mol), start stirring and be slowly heated to 135 DEG C with oil bath,
And it is incubated 6 hours.Then remove oil bath, be cooled to 50 DEG C, in flask, add 200g water, continue stirring 1 little
Time.Then by the buchner funnel sucking filtration of material in flask, gained filtering residue transfers in drying baker drying under reduced pressure to constant weight,
Obtain 242.7g yellowish hydroxyl benzal bisphosphonate product, yield 90.24%.
Embodiment 6
105.4g is added to the there-necked flask equipped with mechanical agitation, thermometer, spherical condensation tube (above connecing offgas duct)
Benzenecarbonyl chloride. (0.75mol) and 123.0g phosphorous acid (0.75mol), start stirring and be slowly heated to 140 DEG C with oil bath,
And it is incubated 7 hours.Then remove oil bath, be cooled to 60 DEG C, in flask, add 180g water, continue stirring 1.5
Hour.Then by the buchner funnel sucking filtration of material in flask, gained filtering residue transfers in drying baker drying under reduced pressure to constant weight,
Obtain 178.9g flaxen hydroxyl benzal bisphosphonate product, yield 88.73%.
Embodiment 7
126.5g is added to the there-necked flask equipped with mechanical agitation, thermometer, spherical condensation tube (above connecing offgas duct)
Benzenecarbonyl chloride. (0.9mol) and 147.6g phosphorous acid (0.9mol), start stirring and be slowly heated to 150 DEG C with oil bath,
And it is incubated 4.5 hours.Then remove oil bath, be cooled to 40 DEG C, in flask, add 160g water, continue stirring 0.5
Hour.Then by the buchner funnel sucking filtration of material in flask, gained filtering residue transfers in drying baker drying under reduced pressure to constant weight,
Obtain 220.3g lurid hydroxyl benzal bisphosphonate product, yield 91.04%.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the restriction for the present invention, this Shen
Embodiment in please and the feature in embodiment, can mutual combination in any in the case of not conflicting.The guarantor of the present invention
The scope of protecting should with claim record technical scheme, including claim record technical scheme in technical characteristic etc.
It is protection domain with alternative.Equivalent the most in this range is improved, also within protection scope of the present invention.
Claims (7)
1. a hydroxyl benzal di 2 ethylhexyl phosphonic acid, it is characterised in that: described hydroxyl benzal di 2 ethylhexyl phosphonic acid structural formula is as described below:
2. the method making hydroxyl benzal di 2 ethylhexyl phosphonic acid described in claim 1, it is characterised in that described method include with
Lower step:
1) phosphorous acid and Benzenecarbonyl chloride. are joined in reaction bulb, open condensation reflux unit and agitating device, slowly
It is warmed up to condensation temp, and insulation carries out condensation reaction, obtains material 1；
2), after material 1 cooling, add water and be hydrolyzed reaction, obtain material 2；
3), after material 2 cooling, use buchner funnel sucking filtration, then gained filtering residue is transferred in vacuum drying oven decompression dry
Dry, obtain white crystal；
Complete the making of hydroxyl benzal di 2 ethylhexyl phosphonic acid.
Method the most according to claim 2, it is characterised in that: described step 1) Benzenecarbonyl chloride. and phosphorous acid
Proportioning mol ratio is 1:1～2.
Method the most according to claim 2, it is characterised in that: described step 1) condensation reaction pressure is normal pressure
Or tiny structure, described tiny structure parameter is 0～10mmHg, and setting-up point is 130～160 DEG C, the response time
It it is 5～8 hours.
Method the most according to claim 2, it is characterised in that: described step 2) add the water yield be material 1
2～3 times of quality.
Method the most according to claim 2, it is characterised in that: described step 2) material 1 be cooled to 40～
60 DEG C, add water hydrolysis, and hydrolysis temperature controls at 45～55 DEG C, and hydrolysis time is 1～2 hour.
Method the most according to claim 2, it is characterised in that: described step 3) drying under reduced pressure condition is,
60～90 DEG C, drying under reduced pressure 5～10 hours under 600～750mmHg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390611.0A CN105906663B (en) | 2016-06-03 | 2016-06-03 | A kind of hydroxyl benzal di 2 ethylhexyl phosphonic acid and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390611.0A CN105906663B (en) | 2016-06-03 | 2016-06-03 | A kind of hydroxyl benzal di 2 ethylhexyl phosphonic acid and preparation method thereof |
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| CN105906663B CN105906663B (en) | 2018-03-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030036537A1 (en) * | 2001-07-16 | 2003-02-20 | Marc Lecouvey | Bisphosphonate derivatives, their preparations and uses |
| CN104478924A (en) * | 2014-12-15 | 2015-04-01 | 常州大学 | 'One-step process' synthetic method of hydroxyethylidene diphosphonic acid |
| CN104603330A (en) * | 2011-12-15 | 2015-05-06 | 索尔维公司 | Process and catalyst for electrochemical reduction of carbon dioxide |
-
2016
- 2016-06-03 CN CN201610390611.0A patent/CN105906663B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030036537A1 (en) * | 2001-07-16 | 2003-02-20 | Marc Lecouvey | Bisphosphonate derivatives, their preparations and uses |
| CN104603330A (en) * | 2011-12-15 | 2015-05-06 | 索尔维公司 | Process and catalyst for electrochemical reduction of carbon dioxide |
| CN104478924A (en) * | 2014-12-15 | 2015-04-01 | 常州大学 | 'One-step process' synthetic method of hydroxyethylidene diphosphonic acid |
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| CN105906663B (en) | 2018-03-02 |
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Denomination of invention: Hydroxybenzylidene diphosphonic acid and its preparation method Effective date of registration: 20220722 Granted publication date: 20180302 Pledgee: Bank of China Limited by Share Ltd. Three Gorges Branch Pledgor: YIDU JOVIAN INDUSTRY CO.,LTD. Registration number: Y2022420000231 |
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Granted publication date: 20180302 Pledgee: Bank of China Limited by Share Ltd. Three Gorges Branch Pledgor: YIDU JOVIAN INDUSTRY CO.,LTD. Registration number: Y2022420000231 |
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