CN105017053B - Synthesis method of salicylamide - Google Patents
Synthesis method of salicylamide Download PDFInfo
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- CN105017053B CN105017053B CN201510418089.8A CN201510418089A CN105017053B CN 105017053 B CN105017053 B CN 105017053B CN 201510418089 A CN201510418089 A CN 201510418089A CN 105017053 B CN105017053 B CN 105017053B
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- Prior art keywords
- salicylamide
- anhydrous
- ptcl
- reaction
- chlorobenzene
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- SKZKKFZAGNVIMN-UHFFFAOYSA-N Salicilamide Chemical compound NC(=O)C1=CC=CC=C1O SKZKKFZAGNVIMN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229960000581 salicylamide Drugs 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 12
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 229910019029 PtCl4 Inorganic materials 0.000 claims abstract description 4
- 239000003208 petroleum Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 5
- STVVMTBJNDTZBF-SECBINFHSA-N (2r)-2-amino-3-phenylpropan-1-ol Chemical compound OC[C@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-SECBINFHSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000284 extract Substances 0.000 abstract description 3
- IJXJGQCXFSSHNL-QMMMGPOBSA-N (R)-(-)-2-Phenylglycinol Chemical compound OC[C@H](N)C1=CC=CC=C1 IJXJGQCXFSSHNL-QMMMGPOBSA-N 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003480 eluent Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 abstract 1
- 229910002027 silica gel Inorganic materials 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 208000006820 Arthralgia Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- GUFGBPFTICJYDD-UHFFFAOYSA-L [Cl-].[Zn+2].O1C=NCC1.[Cl-] Chemical compound [Cl-].[Zn+2].O1C=NCC1.[Cl-] GUFGBPFTICJYDD-UHFFFAOYSA-L 0.000 description 1
- 239000003907 antipyretic analgesic agent Substances 0.000 description 1
- GNHQSAUHXKRQMC-UHFFFAOYSA-N benzene;chlorine Chemical compound [Cl].C1=CC=CC=C1 GNHQSAUHXKRQMC-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- -1 lewis acid platinum tetrachloride Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- 208000004296 neuralgia Diseases 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for synthesizing salicylamide from o-hydroxy benzonitrile and D-phenylglycinol in chlorobenzene solvent in the presence of catalyst (anhydrous PtCl)4When the reaction is carried out for 72 hours under the anhydrous and oxygen-free conditions, PtCl4Amount of (A) to be used39.8 mol% of the raw material, removing chlorobenzene after the reaction is finished, adding 40mL of water, stirring for dissolving, extracting with chloroform, drying and desolventizing an extract phase, separating with a silica gel chromatographic column, and mixing the extract phase with petroleum ether/dichloromethane according to a volume ratio of 1: 100, collecting the final component point, and removing the eluent to obtain the target product salicylamide.
Description
One, technical field
The present invention relates to the preparation method of a kind of organic fine chemicals, be exactly the synthesis side of a kind of salicylamide
Method.
Two, background technology
Salicylamide is antipyretic analgesic, for fever and headache, neuralgia, arthralgia and activeness rheumatism etc..Simultaneously
Also it is the intermediate of the fine chemicals such as other medicine, pesticide.The synthetic method of salicylamide existing many document reports in recent years
Road, logical custom catalysts obtains after being added pyrohydrolysis by salicylonitrile.【1-3】
List of references:
1.Kiss, Arpad; Hell, Zoltan, A heterogeneous catalytic method for the conversion of nitriles into amides using molecular sieves modified with copper(II), Tetrahedron Letters, 2011, 52(45), Pages 6021-6023.
2.By Garcia-Alvarez, Rocio et al, Arene-Ruthenium(II) Complexes Containing Inexpensive
Tris(dimethylamino)phosphine: Highly Efficient Catalysts for the
Selective Hydration of Nitriles into
Amides, Organometallics, 2011, 30(20), 5442-5451.
3.Cadierno, Victorio et al, Bis(allyl)ruthenium(IV) Complexes Containing Water-Soluble Phosphane Ligands: Synthesis, Structure, and Application as Catalysts in the Selective Hydration of Organonitriles into Amides, 2010, Chemistry--A European Journal, 2010, 16(32), 9808-9817.
Applicant, in the experiment with one pot process oxazoline-zinc chloride coordination compound, has unexpectedly obtained another kind ofization
Compound salicylamide.
Three, summary of the invention
It is desirable to provide compound salicylamide, to be solved technical problem is that one-step synthesis obtains target and produces
Thing.
This synthetic method includes synthesis and separates, and described synthesis is salicylonitrile with D-phenylalaninol at chlorobenzene
Solvent has the anhydrous PtCl of catalyst4In the presence of under the conditions of anhydrous and oxygen-free back flow reaction 60 ~ 70 hours, PtCl4Consumption be former
39.8 mol % of doses；
Reaction is sloughed chlorobenzene after terminating, is added 40mL water stirring and dissolving, then extracts with chloroform, after extraction phase drying, precipitation
Upper silica gel column chromatography separates, and is 1:100 eluting by volume with petroleum ether/dichloromethane, collects last component point, slough eluting
Target product salicylamide is obtained after agent.
Synthetic reaction is as follows:
This synthetic method one step obtains target product, and technique is simple, easy to operate.
This reaction mechanism can be speculated as salicylonitrile under the strong lewis acid platinum tetrachloride effect of 39.8 mol%,
Meeting hydrone and carry out nucleophilic addition, product is salicylamide.
Four, accompanying drawing explanation
Fig. 1 is the X-diffraction analysis figure of salicylamide.
Bond distance's data of crystal:
O(1)-C(1) 1.352(5)
O(2)-C(7) 1.248(4)
C(1)-C(6) 1.387(5)
C(1)-C(2) 1.388(6)
C(2)-C(3) 1.367(6)
C(3)-C(4) 1.371(6)
C(4)-C(5) 1.366(6)
C(5)-C(6) 1.400(5)
C(6)-C(7) 1.471(5)
The bond angle data of crystal
O(1)-C(1)-C(6) 122.0(3)
O(1)-C(1)-C(2) 117.6(3)
C(6)-C(1)-C(2) 120.4(3)
C(3)-C(2)-C(1) 120.2(4)
C(1)-C(6)-C(5) 117.9(3)
C(1)-C(6)-C(7) 119.4(3)
C(5)-C(6)-C(7) 122.8(3)
O(2)-C(7)-N(1) 119.7(3)
O(2)-C(7)-C(6) 120.2(3)
N(1)-C(7)-C(6) 120.1(3)
Five, detailed description of the invention
In 100mL two-mouth bottle, under the conditions of anhydrous and oxygen-free, add anhydrous PtCl4 1.2952g (3.84mmol), 40ml chlorine
Benzene, salicylonitrile 1.1483g (9.64mmol), D-phenylalaninol 2.4897 g, at high temperature reflux mixture
72h, stopped reaction, reduce pressure to remove solvent, residue is used 30mL water dissolution, and uses CHCl3(20mLx2) extraction, organic
Being dried with anhydrous sodium sulfate, rotate and remove solvent, upper silica gel column chromatography column separating purification, by petroleum ether/dichloromethane (volume ratio
1:9) mixed liquor eluting, collects last component point, sloughs eluant and obtains target product salicylamide.Productivity: 20%；m.p.:
139-142℃; 1HNMR (500MHz, CDCl3, 27 DEG C), δ (ppm)=6.84～7.71 (m, 4H), 5.96 (s,
2H)。IR (KBr, cm-1) : 3397(s), 1675(s), 1590(m), 1492(m), 1447(m), 1304(w),
1082(w), 951(w), 751(w); HRMS(EI):m/z (%): calcd for C7H7NO2: 137.0477; found:
137.0481；
The crystal structure determination of compound:
The monocrystalline choosing suitable size under the microscope at room temperature carries out X-ray single crystal diffraction experiment, at 296 (2) k
At a temperature of, on the X-ray single crystal diffractometer of Oxford, with the MoKa ray (λ=0.71073) through graphite monochromator monochromatization
Diffraction data is collected with ω-θ scan mode.The data obtained carries out the Lp factor and empirical absorption correction, and crystal structure is by directly
Method solves, and diffraction data reduction and structure elucidation work use SAINT-5.0 and SHELXS-97 program to complete respectively.Number of crystals
According to as follows:
Match crystal volume data is as follows:
Empirical formula C7H72NO2
Molecular weight 137.14
Temperature 296 (2) K
Wavelength 0.71073
Crystallographic system, space group monocline C2/c
Cell parameter a=24.357 (7) α=90 °.
B=4.9650 (14) β=120.557(11) °.
c = 12.857(5) Å γ = 90°.
Volume 1338.9(8) ^3
Charge density 8,1.361 Mg/m^3
Absorption correction parameter 0.101 mm^-1
Number of electrons 576 in unit cell
Crystal size 0.180x 0.120x 0.050 mm
Scope 1.942 to 25.996 at Theta angle
Index capture range-28≤h≤30 of HKL ,-6 < k < 6 ,-15 < l≤15
Collection/independent diffraction data 4545/ 1313 [R (int)=0.1286]
Data integrity degree 100.0 % of theta=30.5
The method Multi Slice Mode of absorption correction
Transmitance 0.7456 and 0.6049 of minimax
The Matrix least square method of method F^2 that refine uses
Number/number of parameters 1313/0/101 that data number/use limits
The method 0.950 that refine uses
The concordance factor R 1=0.0453 of point diffraction, ω R2=0.0982
The identical factor R 1=0.1067 of observable diffraction, ω R2=0.1268
Absolute configuration parameter 0.0029(12)
Maximum summit on difference Fourier figure and peak valley 0.209 and-0.165e. ^-3
Crystal typical bond distance data:
N(1)-C(7) 1.329(3)
N(1)-H(1A) 0.94(3)
N(1)-H(1B) 0.95(3)
O(1)-C(1) 1.352(3)
O(1)-H(1) 0.8200
O(2)-C(7) 1.248(3)
C(1)-C(2) 1.381(3)
C(1)-C(6) 1.400(3)
C(2)-C(3) 1.364(4)
C(2)-H(2) 0.9300
C(3)-C(4) 1.373(4)
C(3)-H(3) 0.9300
C(4)-C(5) 1.368(3)
C(4)-H(4) 0.9300
C(5)-C(6) 1.382(3)
C(5)-H(5) 0.9300
C(6)-C(7) 1.478(3)
Crystal typical bond angle data:
C(7)-N(1)-H(1A) 119.2(15)
C(7)-N(1)-H(1B) 118.8(15)
H(1A)-N(1)-H(1B) 122(2)
C(1)-O(1)-H(1) 109.5
O(1)-C(1)-C(2) 118.2(2)
O(1)-C(1)-C(6) 121.6(2)
C(2)-C(1)-C(6) 120.2(2)
C(3)-C(2)-C(1) 120.4(2)
C(3)-C(2)-H(2) 119.8
C(1)-C(2)-H(2) 119.8
C(2)-C(3)-C(4) 120.3(3)
C(2)-C(3)-H(3) 119.8
C(4)-C(3)-H(3) 119.8
C(5)-C(4)-C(3) 119.4(3)
C(5)-C(4)-H(4) 120.3
C(3)-C(4)-H(4) 120.3
C(4)-C(5)-C(6) 122.1(2)
C(4)-C(5)-H(5) 119.0
C(6)-C(5)-H(5) 119.0
C(5)-C(6)-C(1) 117.5(2)
C(5)-C(6)-C(7) 123.7(2)
C(1)-C(6)-C(7) 118.8(2)
O(2)-C(7)-N(1) 120.1(2)
O(2)-C(7)-C(6) 120.6(2)
N(1)-C(7)-C(6) 119.4(2)
Claims (1)
1. a synthetic method for salicylamide, including synthesis and separation, it is characterised in that: described synthesis is o-hydroxy first
Nitrile and D-phenylalaninol, in chlorobenzene solvent, have the anhydrous PtCl of catalyst4In the presence of under the conditions of anhydrous and oxygen-free back flow reaction 72
Hour, PtCl4The 39.8 mol % that consumption is material quantity, reaction sloughs chlorobenzene, adds 40mL water stirring and dissolving after terminating, then
Extracting with chloroform, after extraction phase drying, precipitation, upper silica gel column chromatography separates, and is 1 by volume with petroleum ether/dichloromethane:
100 eluting, collect last component point, obtain target product salicylamide after sloughing eluant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418089.8A CN105017053B (en) | 2015-07-16 | 2015-07-16 | Synthesis method of salicylamide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510418089.8A CN105017053B (en) | 2015-07-16 | 2015-07-16 | Synthesis method of salicylamide |
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| Publication Number | Publication Date |
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| CN105017053A CN105017053A (en) | 2015-11-04 |
| CN105017053B true CN105017053B (en) | 2016-11-16 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8904799D0 (en) * | 1989-03-02 | 1989-04-12 | Interox Chemicals Ltd | Amide preparation |
| CN102267954A (en) * | 2011-06-13 | 2011-12-07 | 罗梅 | Chiral oxazoline and synthetic method thereof |
| CN102807504B (en) * | 2012-09-01 | 2014-01-15 | 罗梅 | Method for synthesizing salicylamide |
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