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CAS No. : | 33100-27-5 | MDL No. : | MFCD00005110 |
Formula : | C10H20O5 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | VFTFKUDGYRBSAL-UHFFFAOYSA-N |
M.W : | 220.26 | Pubchem ID : | 36336 |
Synonyms : |
|
Num. heavy atoms : | 15 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 1.0 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 5.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 53.49 |
TPSA : | 46.15 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | Yes |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -7.98 cm/s |
Log Po/w (iLOGP) : | 2.2 |
Log Po/w (XLOGP3) : | -0.48 |
Log Po/w (WLOGP) : | 0.08 |
Log Po/w (MLOGP) : | -1.04 |
Log Po/w (SILICOS-IT) : | 1.6 |
Consensus Log Po/w : | 0.47 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.9 |
Solubility : | 27.5 mg/ml ; 0.125 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.02 |
Solubility : | 209.0 mg/ml ; 0.95 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -1.37 |
Solubility : | 9.33 mg/ml ; 0.0424 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 3.06 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium ion In methanol at 25℃; complexing ability and selectivity to sodium cation; | ||
With potassium ion In methanol at 25℃; | ||
With potassium chloride In methanol at 25℃; |
With potassium chloride In methanol at 25℃; ΔG0, ΔH0, ΔS0; reaction in water; enthalpy-entropy compensation for the complexation reactions of crown ethers with alkaline cations; | ||
With potassium ion In acetonitrile at 25℃; | ||
With potassium ion In gas at 76.9℃; | ||
With lithium perchlorate In acetone at 25℃; -ΔH, TΔS; complexation of alkali metal cations (Li+, Na+, K+, Rb+, Cs+) with crown ethers, diaza crown ethers and cryptands in acetone, stability constants of complexes formed; influence of ion-pair formation on stability constants; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium cation In methanol at 25℃; complexing ability and selectivity to sodium cation; | ||
With sodium cation In methanol at 25℃; | ||
With sodium chloride In methanol at 25℃; |
With sodium chloride In methanol at 25℃; ΔG0, ΔH0, ΔS0; reaction in water; enthalpy-entropy compensation for the complexation reactions of crown ethers with alkaline cations; | ||
With sodium cation In acetonitrile at 25℃; | ||
With sodium cation In gas at 76.9℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 58% 2: 31% | With di-tert-butyl peroxide In benzene at 20℃; for 48h; Irradiation; Further byproducts given; | |
15% | With dihydrogen peroxide; iron(II) sulfate In water at 0℃; for 1h; Further byproducts given. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 1.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With nickel In diethyl ether; dichloromethane at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With triethylamine pentahydrogen fluoride salt In acetonitrile at 20℃; Electrochemical reaction; anodic oxidation; platinum plate electrodes; 10 mA/cm2 constant current; 6 F/mol; | |
90% | With triethylamine pentahydrogen fluoride salt In acetonitrile at 20℃; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium In tetrahydrofuran at -20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60.7% | With cesium fluoride In 1,2-dimethoxyethane at -20 - 20℃; for 15h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | Stage #1: tetrakis(di-tert-butyldimethylsilyl)disilene With sodium naphthalenide In tetrahydrofuran at -78 - 20℃; Stage #2: 15-crown-5 In tetrahydrofuran at 20℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride In tetrahydrofuran; diethyl ether; dichloromethane; mineral oil | 1 EXAMPLE 1 EXAMPLE 1 A mixture of 1-[3-(naphth-2-ylmethoxy)phenyl]cyclohexanol (0.65 g), sodium hydride (0.096 g of a 50% w/w dispersion in mineral oil), 1,4,7,10,13-pentaoxacyclopentadecane (hereinafter 15-crown-5, (0.06 g) and tetrahydrofuran (10 ml) was stirred at ambient temperature for 15 minutes. methyl iodide (0.12 ml) was added and the mixture was stirred at ambient temperature for 15 hours. The mixture was evaporated and the residue was partitioned between diethyl ether and water. The organic layer was separated, washed with a saturated aqueous sodium chloride solution, dried (MgSO4 and evaporated. The residue was purified by column chromatography using a 9:1 v/v mixture of methylene chloride and diethyl ether as eluent. There was thus obtained 1-methoxy-1-[3-(naphth-2-ylmethoxy)phenyl]cyclohexane (0.35 g, 54%), m.p. 74-75°C. The 1-[3-(naphth-2-ylmethoxy)phenyl]cyclohexanol starting material was obtained as follows:-. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In water; ethyl acetate; N,N-dimethyl-formamide; | EXAMPLE 3 Production of 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methylsulfenyl-5-(1-oxy-pyridin-3-ylmethylamino)pyrazole-3-carbonitrile (Compound No. 14) In 10 ml of N,N-dimethylformamide was suspended 0.1 g of 60% sodium hydride, and 1 g of 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile was gradually added thereto. After 20 minutes of stirring at room temperature, 3 drops of 15-crown-5-ether and then 0.3 g of 3-chloromethylpyridine-1-oxide were added thereto, followed by stirring at room temperature. After standing over one night, water and ethyl acetate were added thereto and the mixture was neutralized by 1N hydrochloric acid. After liquid separation, the organic layer was washed with saturated saline and then dried over anhydrous sodium sulfate. The residue was purified by a silica gel column chromatography to obtain 0.9 g of the compound (No. 14) described in the following Table 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In acetonitrile | Synthesis of N-[3-chloro-2-(hydroxyimino)-3-methylbutyl]-2-nitroimidazole (Compound IX) To the sodium salt of 2-nitroimidazole prepared above was added acetonitrile (50 ml), 15-crown-5-ether (3.5 ml, 14.3 mmol) and 4-bromo-2-methyl-2-butene (2 ml; 17.4 mmol). The mixture was stirred at RT for ca 16 h. and then the solvent was removed to leave a crude semi-solid which was purified by column chromatography on silica. The intermediate product, 1-(3-methyl-2-butenyl)-2-nitroimidazole (80% yield) was eluted using a mixture of petroleum ether (40-60)/ethyl acetate (ratio 4:1 respectively). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In <i>N</i>-methyl-acetamide; mineral oil | 1 EXAMPLE 1 A mixture of 2-(3-methoxymethoxyphenyl)butane-1,2-diol (16.3 g), sodium hydride (8.74 g of a 50% w/w dispersion in mineral oil) and dimethylformamide (160 ml) was stirred at ambient temperature for 15 minutes. Methyl iodide (41.3 g) and 1,4,7,10,13-pentaoxacyclopentadecane (hereinafter 15-crown-5, 0.5 g) were added and the mixture was stirred at ambient temperature for 15 hours. The mixture was evaporated and the residue was partitioned between methylene chloride and water. The organic layer was separated, washed with water, dried (MgSO4) and evaporated. There was thus obtained 2-methoxy-2-(3-methoxymethoxyphenyl)but-1-yl methyl ether as an oil (16.3 g, 95%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In tetrahydrofuran; N,N-dimethyl-formamide; mineral oil | 6 EXAMPLE 6 Sodium hydride (60% dispersion in mineral oil, 0.14 g) was added portionwise to a stirred solution of a portion (0.87 g) of the 3-hydroxypyrrolidine so obtained and 1,4,7,10,13-pentaoxacyclopentadecane (hereinafter 15-crown-5, 0.05 g) in DMF (10 ml). The mixture was stirred at ambient temperature for 15 minutes. A solution of methyl 4-toluenesulphonate (0-56 g) in THF (2 ml) was added dropwise and the mixture was stirred at ambient temperature for 2 hours. The mixture was partitioned between diethyl ether and water. The organic phase was dried (Na2 SO4) and evaporated. The residue was purified by column chromatography using increasingly polar mixtures of hexane and ethyl acetate as eluent. There was thus obtained 1-benzyl-3-(3,5-difluorophenyl)-3-methoxypyrrolidine (0.82 g, 90%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In tetrahydrofuran; mineral oil | 18 EXAMPLE 18 The (2S,4R)-4-(tert-butyldimethylsilyloxy)-4-[3-(8-chloro-2-oxo-1,2,3,4-tetrahydroquinolin-6-ylthio)phenyl]-2-methyltetrahydropyran used as a starting material was obtained as follows: Sodium hydride (50% dispersion in mineral oil, 0.3 g) was added portionwise to a stirred mixture of (2S,4R)-4-hydroxy-4-(3-iodophenyl)-2-methyltetrahydropyran (1.64 g), 1,4,7,10,13-pentaoxacyclopentadecane (hereinafter 15-crown-5, 0.05 g) and THF (30 ml) and the mixture was stirred at ambient temperature for 30 minutes. Tert-butyldimethylsilyl chloride (0.9 g) was added and the mixture was stirred and heated to 60° C. for 6 hours. The mixture was cooled to ambient temperature and partitioned between diethyl ether and a dilute aqueous ammonium chloride solution. The organic solution was washed with brine, dried (Na2 SO4) and evaporated. The residue was purified by column chromatography using increasingly polar mixtures of hexane and ethyl acetate as eluent. There was thus obtained (2S,4R)-4-(tert-butyldimethylsilyloxy)-4-(3-iodophenyl)-2-methyltetrahydropyran (1.9 g, 88%) as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In tetrahydrofuran; mineral oil | 1 EXAMPLE 1 EXAMPLE 1 A mixture of 4-hydroxy-4-[3-(naphth-2-ylmethoxy)phenyl]-tetrahydropyran (1.9 g), sodium hydride (0.27 g of a 50% w/w dispersion in mineral oil), 1,4,7,10,13-pentaoxacyclopentadecane (hereinafter 15-crown-5, 0.2 g) and tetrahydrofuran (10 ml) was stirred at ambient temperature for 15 minutes. Methyl iodide (0.35 ml) was added and the mixture was stirred at ambient temperature for 15 hours. The mixture was evaporated and the residue was partitioned between diethyl ether and water. The organic layer was separated, washed with a saturated aqueous sodium chloride solution, dried (MgSO4) and evaporated. The residue was purified by column chromatography using a 9:1 v/v mixture of methylene chloride and diethyl ether as eluent. There was thus obtained 4-methoxy-4-[3-(naphth-2-ylmethoxy)phenyl]tetrahydropyran (1.8 g, 94%), m.p. 66.5°-67.5° C. The 4-hydroxy-4-[3-(naphth-2-ylmethoxy)phenyl]tetrahydropyran starting material was obtained as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With sodium sand In tetrahydrofuran addn. of soln. of (CO)2(PMe3)Fe(μ2-t-Bu2P)(μ2-CO)Rh(PMe3)2 in THF to excess of sodium sand (room temp., under N2 in presence of traces of O2), stirring (4 h), filtration, addn. of 15-crown-5, stirring (room temp., 12 h); removing of volatile material (vac.), washing of residue with hexane (3 times), extn. (diethyl ether), cooling (-20°C, about 1 wk), crystn., collection of crystals, drying (vac.); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
29% | With sodium sand In tetrahydrofuran addn. of soln. of (CO)3(PMe3)Fe(μ2-t-Bu2P)Rh(CO)(PMe3) in THF to excess of sodium sand (room temp., under N2 in presence of traces of O2), stirring (4 h), color change from yellow to red, filtration, addn. of 15-crown-5, stirring (room temp., 12 h); removing of volatile material (vac.), washing of residue with hexane (3 times), extn. (diethyl ether), cooling (-20°C, about 1 wk), crystn., collection of crystals, drying (vac.); elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With AgBF4 In water Ag2C2 added to concd. aq. soln. of AgCF3CO2 and AgBF4; stirred until satn.; excess Ag2C2 filtered off; (15)crown-5 added to filtrate; allowed tostand (several h); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With air In methanol standed in air for 3 wk; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In acetonitrile soln. of (15)crown-5 in MeCN added to soln. of TiF4 in MeCN; concd., stored at room temp. for several h; elem. anal.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol at 50℃; for 3h; | [(15-Crown-5)Na][Br] Used in CORM-365; 1.070 g (4.86 mmol) of 15-Crown-5 (commercially available) and 500 mg (3.78 mmol) of NaBr were stirred together in 15 ml: of methanol at 50° C. for 3 hrs. Following this, the solvent was removed on rotary, evaporator to give a solid product that was washed several times with ether and then dried under vacuum.1.317 g of a white solid was obtained. Yield was 83.9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With tetrabutylammonium decatungstate (TBADT, (nBu4N)4W10O32) In chlorobenzene; acetonitrile at 5 - 10℃; for 0.25h; Inert atmosphere; Irradiation; | |
30% | With benzophenone In 1,2-dichloro-benzene at 50 - 55℃; for 5h; Inert atmosphere; Sealed tube; Irradiation; | 1-({4-[(3,4-Dimethoxyphenyl)(phenyl)methyl]-2-methoxyphenoxy}methyl)-1,2-dihydro[60]fullerene (2a). General procedure: Solution of 60 (150 mg, 0.21 mmol), 1,2-dimethoxy-4-[(3,4-dimethoxyphenyl)-(phenyl)methyl]benzene (1a) (758 mg, 2.1 mmol), BP (1895 mg,10.4 mmol) in DCB (30 mL) was irradiated in a sealed degassed pyrex ampoule at 50-55 C for 21 h. The solvent was removedin vacuo, the residue was washed with hexane and acetone, thenseparated by chromatography on a silica gel column. UnreactedC60 and then compound 2a were eluted with toluene. The solventwas removed in vacuo, the residue was washed with hexane,acetone, and dried in vacuo at 50 C. Compound 2a (68 mg) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium bromide In water at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium hydroxide In water at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With sodium iodate In water at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With sodium azide In acetone at 20℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With benzophenone In acetonitrile at 20℃; for 3h; Inert atmosphere; UV-irradiation; chemoselective reaction; | |
84% | With benzophenone In acetonitrile at 20℃; for 3h; Inert atmosphere; UV-irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With benzophenone In <i>tert</i>-butyl alcohol at 20℃; for 1h; Irradiation; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium azide In water; acetonitrile at 20℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In pentane at 20℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65 mg | Stage #1: 15-crown-5; [In(N,N',N''[2,2',2''nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzene-sulfonamidato))]; sodium hydroxide In tetrahydrofuran at 20℃; for 8h; Inert atmosphere; Stage #2: diethyl ether at 20℃; for 120h; Inert atmosphere; | 2.3.2 [15-crown-5⊃NaI-(μ-OH)-InIIIMST A suspension of H3MST (323mg, 0.467mmol) and NaH (34.7mg, 1.45mmol) in 5mL of DMA was allowed to stir for 45min. After H2 evolution ceased, In(OAc)3 (137mg, 0.469mmol) was added and the solution stirred vigorously. After 2h, 5mL of Et2O was added and the solution stirred for an additional 30min, followed by filtration (see Note). The filtrate was concentrated to dryness under reduced pressure, then the residue was triturated with Et2O and dried to afford a white precipitate. The solid was collected in a medium-porosity glass fritted funnel, washed with Et2O and pentane, and dried in vacuo to yield 356mg (∼90%) of a white powder, which was used without further purification. 1H NMR (500MHz, DMSO-d6, ppm): 2.22 (s, 9H), 2.52 (br t, 6H), 2.58 (s, 18H), 2.80 (br t, 6H), 6.87 (s, 6H). A suspension of this white powder that was assumed to be [InMST] (117mg, 0.145mmol), NaOH (6.3mg, 0.16mmol) and 15-crown-5 (46μL, 0.23mmol) in 4mL THF was allowed to stir for 8h, after which the mixture was filtered with a medium-porosity glass fritted funnel into a vial. Diethyl ether was slowly allowed to diffuse into the vial and within 1day a white powdery residue formed, which was removed via filtration and the filtrate was again exposed to Et2O vapor. Over the next 5days colorless crystals formed, which were collected, washed with Et2O, and dried in vacuo to yield 65mg (40%) of the product. 1H NMR (500MHz, CDCl3, ppm): 1.79 (s, OH), 2.26 (s, 9H), 2.58 (t, 6H), 2.72 (s, 18H), 2.92 (t, 6H), 3.62 (m, 20H), 6.87 (s, 6H). 13C{1H} NMR (500MHz, CDCl3, ppm): 21.0, 23.6, 40.2, 52.9, 69.4, 131.4, 136.5, 139.4, 140.0. FTIR (Nujol, selected bands, cm-1) ν(OH) 3561; 1602, 1563, 1113, 975, 817, 653. Anal. Calc. for [15-crown-5⊃NaI-(μ-OH)-InIIIMST], C47H76InN4NaO13S3: C, 49.24; H, 6.64; N, 5.10. Found: C, 49.56; H, 6.72; N, 4.92%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With sodium t-butanolate In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With Perbenzoic acid; trifluoroacetic acid In 1,2-dichloro-ethane at 35 - 40℃; for 23h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With Perbenzoic acid; trifluoroacetic acid In 1,2-dichloro-ethane at 35 - 40℃; for 23h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | Stage #1: 15-crown-5; (2S)N-(acetoxymethyl)-N-[(1R,2S,5R)-menthyloxycarbonyl]-2-(2-oxoethyl)glycine methyl ester With triethylamine In 1,2-dichloro-ethane at 26℃; for 0.166667h; Stage #2: With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane for 2.5h; | 2 [0083] (S) N-(Acetoxymethyl)-N-[(1R,2S,5R)-menthyloxycarbonyl]-4-(1,4,7,10-tetraoxa-13-azacyclopentadecan-13-yl)homoalanine methyl ester (53): A solution of the aldehyde (40) (78 mg, 0.20 mmol) in dry dichloroethane (3 mL) wastreated with 1-aza-15-crown-5 (58 mg, 0.26 mmol) and triethylamine (38 mL, 0.27 mmol) and stirred for 10 min. at 26°C. Then sodium (triacetoxy)borohydride (69 mg, 0.32 mmol) was added and the stirring continued for 2.5 h. After usualwork-up and concentration, the residue was purified by rotatory chromatography (hexane/EtOAc, 98:2), yielding theproduct (53) (108 mg, 91%) as a yellowish slurry: [α]D =-51.22 (c 0.41, CHCl3); 1H NMR (500 MHz, CDCl3, 70 °C) δH0.77 (3H, d, J = 6.9 Hz, Me), 0.80-0.90 (1 H, m, 4’-Ha), 0.88 (3H, d, J = 7.3 Hz, Me), 0.89 (3H, d, J = 6.6 Hz, Me), 0.96(1 H, m, 6’-Hb), 1.05 (1 H, m, 3’-Ha), 1.36 (1 H, m, 2’-H), 1.55 (1 H, m, 5’-H), 1.62-1.69 (2H, m, 4’-Hb + 3’-Hb), 1.86 (1H, m, 2"-H), 1.96 (1 H, m, 3-Ha), 2.00 (3H, s, Ac), 2.02 (1 H, m, 6’-Ha), 2.23 (1 H, m, 3-Hb), 2.57-2.69 (2H, m, 4-H2),2.72-2.82 (4H, m, 2 x CH2N), 3.58-3.64 (16H, m, 8 x CH2O), 3.66 (3H, s, OMe), 4.52 (1 H, br b, 2-H), 4.60 (1 H, ddd, J= 4.4, 10.8, 11.0 Hz, 1’-H), 5.35 (1 H, br d, J = 11.0 Hz, OCHaN), 5.45 (1 H, d, J = 11.0 Hz, OCHbN); 13C NMR (125.7MHz, CDCl3, 70 °C) δC 16.3 (CH3), 20.7 (CH3), 21.8 (CH3), 23.6 (CH2), 25.9 (CH), 28.0 (CH2), 31.4 (CH), 34.3 (CH2),41.1 (CH2), 47.4 (CH), 51.9 (CH3), 53.0 (CH2), 54.7 (2 x CH2), 58.3 (CH), 69.8 (2 x CH2), 70.3 (2 x CH2), 70.6 (2 x CH2),71.1 (2 x CH2), 76.7 (CH), 155.3 (C), 170.3 (C), 171.7 (C); MS (EI) m/z (relative intensity) 588 (M+, 1), 545 (M+ - CHMe2, 2), 529 (M+ - OAc, 4), 232 ([1-methylen-1-aza-15-crown-5]+, 100. HRMS calcd for C29H52N2O10, 588.3622, found588.3626; calculated for C26H45N2O10, 545.3074, found 545.3077; calculated for C25H41N2O10, 529.2761, found529.2758; calculated for C11H22NO4, 232.1549, found 232.1542. Elemental analysis: Calculated for C29H52N2O10: C,59.16; H, 8.90; N, 4.76; found C, 59.24; H, 8.90; N, 4.88. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 20℃; | General procedure: Crystals of compounds 1-3 were prepared by isothermal evaporation fromaqueous solutions at room temperature. The crystals of compound 1 weresynthesized by the reaction of 0.051 g (0.1 mmol) of UO2(NO3)2·6H2O,0.040 g (0.22 mmol) of 12-crown-4, 0.280 g (2.0 mmol) of 40% H2SeO4,and 2.001 g (111.2 mmol) of deionized distilled water. Compound 2:0.050 g (0.1 mmol) of uranyl nitrate, 0.046 g (0.21 mmol) of 15-crown-5,0.282 g (2.0 mmol) of selenic acid, and 2.012 g (111.7 mmol) of deionizeddistilled water. Compound 3: 0.050 g (0.1 mmol) of uranyl nitrate, 0.046 g(0.21 mmol) of 15-crown-5, 0.282 g (2.0 mmol) of selenic acid, and 2.012 g(111.7 mmol) of deionized distilled water (note: the bulk of crystals herebelongs to compound 2). Homogeneous liquid solutions were left in awatch glass. Yellowish-green flattened crystals formed within 2 weeks. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 20℃; | General procedure: Crystals of compounds 1-3 were prepared by isothermal evaporation fromaqueous solutions at room temperature. The crystals of compound 1 weresynthesized by the reaction of 0.051 g (0.1 mmol) of UO2(NO3)2·6H2O,0.040 g (0.22 mmol) of 12-crown-4, 0.280 g (2.0 mmol) of 40% H2SeO4,and 2.001 g (111.2 mmol) of deionized distilled water. Compound 2:0.050 g (0.1 mmol) of uranyl nitrate, 0.046 g (0.21 mmol) of 15-crown-5,0.282 g (2.0 mmol) of selenic acid, and 2.012 g (111.7 mmol) of deionizeddistilled water. Compound 3: 0.050 g (0.1 mmol) of uranyl nitrate, 0.046 g(0.21 mmol) of 15-crown-5, 0.282 g (2.0 mmol) of selenic acid, and 2.012 g(111.7 mmol) of deionized distilled water (note: the bulk of crystals herebelongs to compound 2). Homogeneous liquid solutions were left in awatch glass. Yellowish-green flattened crystals formed within 2 weeks. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With mercury In tetrahydrofuran at 20℃; for 6h; Inert atmosphere; Schlenk technique; Glovebox; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol at 50 - 60℃; for 1h; | Preparation of 15-crown-5 complexes General procedure: A solution of (2 mmol, 0.4 ml) of 15-crown-5 in (10 ml) of absolute ethanol was added to a solution of (1 mmol, 0.933 gm Pr-picrate), (0.936 gm Nd-picrate) and (0.900 gm Dy-picrate) in (10 ml) of absolute ethanol and refluxed at (50 - 60 oC) for (1 hr.). The solution was concentrated at (40 - 50 oC) to a very small volume (till the formation of a precipitate), usually a gummy precipitate forms which was treated with (40 - 60 oC) petroleum ether until all the gummy precipitate was converted to a fine yellow - orange powder. The precipitate was collected and stored in a desicator for complete dryness. These complexes were also prepared by another method, by stirring a solution of 15-crown-5 with a solution of lanthanide picrate for (24 - 48 hrs.). The gummy precipitates were treated with petroleum ether. The yields were (92 - 96%)24. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol at 50 - 60℃; for 1h; | Preparation of 15-crown-5 complexes General procedure: A solution of (2 mmol, 0.4 ml) of 15-crown-5 in (10 ml) of absolute ethanol was added to a solution of (1 mmol, 0.933 gm Pr-picrate), (0.936 gm Nd-picrate) and (0.900 gm Dy-picrate) in (10 ml) of absolute ethanol and refluxed at (50 - 60 oC) for (1 hr.). The solution was concentrated at (40 - 50 oC) to a very small volume (till the formation of a precipitate), usually a gummy precipitate forms which was treated with (40 - 60 oC) petroleum ether until all the gummy precipitate was converted to a fine yellow - orange powder. The precipitate was collected and stored in a desicator for complete dryness. These complexes were also prepared by another method, by stirring a solution of 15-crown-5 with a solution of lanthanide picrate for (24 - 48 hrs.). The gummy precipitates were treated with petroleum ether. The yields were (92 - 96%)24. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol at 50 - 60℃; for 1h; | Preparation of 15-crown-5 complexes General procedure: A solution of (2 mmol, 0.4 ml) of 15-crown-5 in (10 ml) of absolute ethanol was added to a solution of (1 mmol, 0.933 gm Pr-picrate), (0.936 gm Nd-picrate) and (0.900 gm Dy-picrate) in (10 ml) of absolute ethanol and refluxed at (50 - 60 oC) for (1 hr.). The solution was concentrated at (40 - 50 oC) to a very small volume (till the formation of a precipitate), usually a gummy precipitate forms which was treated with (40 - 60 oC) petroleum ether until all the gummy precipitate was converted to a fine yellow - orange powder. The precipitate was collected and stored in a desicator for complete dryness. These complexes were also prepared by another method, by stirring a solution of 15-crown-5 with a solution of lanthanide picrate for (24 - 48 hrs.). The gummy precipitates were treated with petroleum ether. The yields were (92 - 96%)24. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In 1,4-dioxane; 1,2-dichloro-ethane at 60 - 180℃; Large scale; | 1 Step one, according to the vacuum system operating steps to open and close the relevant valves and buttons,240 kg of triethylene glycol and 1200 kg of dioxane into the 3000L stainless steel reactor,Stir for 5 minutes to make the mixture even;Step two, 600 kg of dichloroethyl ether and 330 kg of dioxane into the high slot,After pumping off the first vacuum system, and then open the relevant valve,So that the entire reaction system into a reflow device, and the pumping port closed;Step 3: Stirring the triethylene glycol and dioxane in step 1,Open the manhole cover, the 190 kg of sodium hydroxide slowly into the 3000L stainless steel reactor,Plus cover after the full hole cover;Step four, open the stir, about 5 minutes later,After the temperature of the whole reaction system is constant,Then slowly add steam to 60 , and keep for 15 minutes;Step five, open the relevant valve,The high-level tank of dichloroethyl ether and dioxane mixture in accordance with the first fast and slow way to drop into the reactor,While controlling the kettle temperature below 60 ;Step six,The mixture of dichloroethene and dioxane as described in step 5 was started,The temperature was maintained at 70 ° C for 24 hours;Step seven, the end of the reaction, first stop heating, and then open the cooling water,After centrifuging at room temperature, the filtrate was obtained;Step 8, open the vacuum system, and then open the relevant valve, the seven steps in the filtrate pumpingInto the stainless steel reactor, and then turn off the vacuum system, open the relevant valve, the system was distillation system,The atmospheric distillation, to the stainless steel reactor temperature of 120 , stop heating, the distillation of the substrate;Step 9. Transfer the distillation substrate obtained in step 8 to a 500L stainless steel distillate and open the oilFurnace system for heating and vacuum distillation, reflux ratio of 10: 1; steam to the kettle 140 , kettle outlet 100 ,The resulting fraction is a pre-fraction, at which time the replacement tank is replaced, and the former fraction is left for other use;Kettle outlet 180 , close the oil furnace system, get product fractions.Step 10, the detection of the product obtained in step 9, after passing the package storage; if not qualified, repeat step9, until the product testing qualified. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | In tetrahydrofuran at 60℃; for 8h; Inert atmosphere; | 2.1 Synthesis of 1 NaN(CN)2 (32 mg, 0.4 mmol) and 15-crown-5 (88 mg, 0.4mmol) were added to 10mL of dry and distilled THF solvent, and this reaction mixture was stirred at 60°C for 8 h under an atmosphere of N2. After filtration, thefiltrate was reduced to 5mL in a small tube, which wasloaded into a large vial containing 5mL of n-hexane. The large vial was sealed and left undisturbed at room temperature. Colorless crystals of 1 formed in 10days. Yield:76%. - C12H20N3NaO5: calcd. C 46.60, H 6.53, N 13.59; foundC 46.53, H 6.48, N 13.12%. - FT-IR (KBr, 4000-400 cm-1): 3515(br, m), 2916(m), 2878(w), 2245(s), 2202(m), 2148(vs), 1623(w), 1473(w), 1353(m), 1324(m), 1289(w), 1245(w), 1117(s), 1089(s), 1038(m), 946(s), 901(w), 862(m), 834(w),524(m). ν (CN) vibrations of dicyanamide anions [22]: 2245 (νas+νs), 2202 (νas), 2148 (νs). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: diphenylthiophosphinic acid With sodium methylate In methanol Stage #2: 15-crown-5; diphenylthiophosphinic acid In dichloromethane at 20℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.2% | With sodium carbonate; dicyclohexyl-carbodiimide In 1,4-dioxane at 70 - 75℃; for 6h; | 1 In 1000 ml of four-mouth bottle is sequentially added in the sodium carbonate (19.4g), dicyclohexyl carbodiimide (103.0g, 0.5 µM) and dioxane (300 ml), stirring and mixing, heating to 70-75 °C, synchronous slow instillment tetraglycol (97.0g, 0.5 µM) of the dioxane (150 ml) solution and ethylene glycol (46.5g, 0 . 75 µM) of the dioxane (50 ml) solution, control drop accelerating-rate, thus the two synchronous drop end, continue to thermal insulation 6h, sampling monitoring to the raw content <1% (GC - Area %), room temperature, the majority of the solvent is removed under reduced pressure, the resulting concentrated pulpiness added to 250 ml of dichloromethane, stir and mix filtering, cake 50 ml of dichloromethane washing, the filtrate and the washing liquid, anhydrous magnesium sulfate after drying for exsolution, the obtained crude product to continue to vacuum distillation, shall be 15-crown ether-5 finished 78.2g, content 98.7%, yield 70.2%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With triethylsilane; di-tert-butyl peroxide; Fe(acac)2 at 20 - 80℃; for 9h; Inert atmosphere; | 19 Example 19 Compound 19:Fe (acac) 2 (6.4 mg, 0.025 mmol) was added sequentially to a 25 mL two-necked flask,Cyclohexanol (31 [mu] L, 0.25 mmol)Triethylsilane (121 [mu] L, 0.75 mmol)Di-tert-butyl peroxide (94 [mu] L, 0.5 mmol)The gas was replaced with dry N2 for 3 times,Finally, dry-dried 15-crown-5 (2.0 mL) was added under N2 protection.The mixture was stirred at room temperature and heated to 80 ° C to carry out the reaction,Until the thin layer chromatography monitoring of raw materials is completed.At the end of the reaction, 15.0 mL of NaCl solution was added at room temperature,Extracted with ether 15.0mL three times, combined with organic phase decompression steaming,The product was purified by column chromatography in 80% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With sodium hexamethyldisilazane In tetrahydrofuran; toluene at 25℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With sodium hexamethyldisilazane In tetrahydrofuran; toluene at 25℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In methanol; acetonitrile at 120℃; High pressure; | 3 Example 3 One mole of molybdenum tetrachloride was placed in a 50 ml round bottom flask containing 15 ml of methanol and 15 ml of acetonitrile,Placed in a magnetic stirrer for 30min,After slowly dropping 30% HCl,Then add 0.5ml15C5 continue stirring 8h to 20h.Filter and pour the filtrate into a 25 ml pressure bomb.120 hydrothermal synthesis of 48h to 72h, filtered to give a light green serum, the clear liquid placed in a long test tube, slowly along the test tube wall to the filtrate twice the height of the seal standing, about a week after the precipitation of light green The crystal, which is the compound [MoCl2O2 (H2O) 2] [15C5], has the same infrared spectrum / elemental analysis and the same molecular and crystal structure as those in Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; water; acetone at 120℃; High pressure; | 11 Example 11 0.8gNa2MoO4 · 2H2O into a 50ml round bottom flask containing 15m of acetone and 15ml of methanol, placed on a magnetic stirrer for 30min, 0.2g of aqueous solution of sodium chloride and 0.5ml of 15C5 was added and stirring was continued for 8h to 20h. Filter and pour the filtrate into a 25 ml pressure bomb. 120 hydrothermal synthesis of 48h to 72h, filtered to give a light green serum, the clear liquid placed in a long test tube, slowly along the test tube wall to the filtrate twice the height of the seal standing, about a week after the precipitation of light green The crystal, which is the compound [MoCl2O2 (H2O) 2] [15C5], has the same infrared spectrum / elemental analysis and the same molecular and crystal structure as those in Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; water; acetone at 120℃; High pressure; | 12 Example 12 0.8gNa2MoO4 · 2H2O into a 50ml round bottom flask containing 15m of acetone and 15ml of methanol, placed on a magnetic stirrer for 30min, 0.2g of aqueous solution of sodium chloride and 0.5ml of 15C5 was added and stirring was continued for 8h to 20h. Filter and pour the filtrate into a 25 ml pressure bomb. 120 hydrothermal synthesis of 48h to 72h, filtered to give a light green serum, the clear liquid placed in a long test tube, slowly along the test tube wall to the filtrate twice the height of the seal standing, about a week after the precipitation of light green The crystal, which is the compound [MoCl2O2 (H2O) 2] [15C5], has the same infrared spectrum / elemental analysis and the same molecular and crystal structure as those in Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; water; acetonitrile at 120℃; High pressure; | 1 Example 1 0.8 g of Na 2 MoO 4 · 2H 2 O was placed in a 50 ml round bottom flask containing 15 ml of anhydrous methanol and 15 ml of acetonitrile,Placed in a magnetic stirrer for 30min,After slowly dropping 30% HCl,Then add 0.5ml15C5 continue stirring 8h to 20h.Filter and pour the filtrate into a 25 ml pressure bomb.120 hydrothermal synthesis of 48h to 72h, filtered to give a light green serum,The supernatant was placed in a long test tube, along the test tube wall slowly added ether to the filtrate twice the height of the seal was allowed to stand, about a week after the precipitation of light green crystals,Namely the compound [MoCl2O2 (H2O) 2] [15C5], the structure is as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; acetone; acetonitrile at 120℃; High pressure; | 6 Example 6 Place 1mol (NH4) 2Mo2O7 · 2H2O into a 50ml round bottom flask containing 15m acetone and 15ml acetonitrile, stir on a magnetic stirrer for 30min, then slowly add 30% HCl, add 0.5ml15C5 and continue stirring for 8h To 20h. Filter and pour the filtrate into a 25 ml pressure bomb. 120 hydrothermal synthesis of 48h to 72h, filtered to give a light green serum, the clear liquid placed in a long test tube, slowly along the test tube wall to the filtrate twice the height of the seal standing, about a week after the precipitation of light green The crystal, which is the compound [MoCl2O2 (H2O) 2] [15C5], has the same infrared spectrum / elemental analysis and the same molecular and crystal structure as those in Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | Stage #1: 1-phenyl-1H-tetrazole-5-thiol With lithium hydroxide In methanol at 20℃; for 2h; Stage #2: 15-crown-5 In methanol for 5h; | 1 2.2.1 [Li(15-crown-5)(SCN4Ph)] (2) LiOH (0.068 g, 2.81 mmol) was added to a solution of 1-phenyl-1-H-tetrazole-5-thione (1) (0.50 g, 2.81 mmol) in methanol (40 mL) at ambient temperature. The solution was stirred for 2 h and then 15-crown-5 ether (1,4,7,10,13-Pentaoxacyclopentadecane) (0.62 g, 2.81 mmol) was added. The reaction mixture was stirred for 5 h and the volume of the solution was reduced and allowed to crystallize. Yield: 88%. Mp: 184-186 °C (dec). IR (KBr): 2913, 2881, 1594, 1496, 1098 (C-O) cm-1. 1H NMR (300 MHz, CDCl3, 25 °C): δ 3.77 (s, 20H, CH2-O), 7.34 (m, 1H, p-ArH), 7.44 (t, 2H, m-ArH), 8.05 (d, 2H, o-ArH) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ 69.0 (C-O), 124.3 (o-C), 127.6 (p-C), 128.8 (m-C), 137.0 (i-C), 167.9 (CS) ppm. MS (FAB+) m/z (%): 227 [Li(15-crown-5)+] (1 0 0), 404 [M+] (15). Anal. Calcd for C17H25LiN4O5S (404.17): C, 50.49; H, 6.19. Found: C, 50.13; H, 6.21. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: 1-phenyl-1H-tetrazole-5-thiol With sodium hydroxide In methanol at 20℃; for 2h; Stage #2: 15-crown-5 In methanol for 5h; | 2 2.2.1 [Li(15-crown-5)(SCN4Ph)] (2) General procedure: LiOH (0.068 g, 2.81 mmol) was added to a solution of 1-phenyl-1-H-tetrazole-5-thione (1) (0.50 g, 2.81 mmol) in methanol (40 mL) at ambient temperature. The solution was stirred for 2 h and then 15-crown-5 ether (1,4,7,10,13-Pentaoxacyclopentadecane) (0.62 g, 2.81 mmol) was added. The reaction mixture was stirred for 5 h and the volume of the solution was reduced and allowed to crystallize. Yield: 88%. 2.2.2 [Na(15-crown-5)(SCN4Ph)] (3) Compound 3 was prepared using the same procedure outlined for 2 starting from 1 (0.50 g, 2.81 mmol), NaOH (0.110 g, 2.81 mmol) and 15-crown-5 ether (0.62 g, 2.81 mmol). Yield: 73% (0.86 g, 2.05 mmol). Mp: 120-122 °C (dec). IR (KBr): 2907, 2871, 1594, 1496, 1119 (C-O) cm-1. 1H NMR (300 MHz, CDCl3, 25 °C): δ 3.66 (m, 20H, CH2-O), 7.25 (m, 1H, p-ArH), 7.33 (m, 2H, m-ArH), 8.00 (m, 2H, o-ArH) ppm. 13C NMR (75 MHz, CDCl3, 25 °C): δ 69.3 (C-O), 123.6 (o-C), 127.7 (p-C), 128.6 (m-C), 136.9 (i-C), 167.0 (CS) ppm. FAB+ m/z (%): 243 [Na(15-crown-5)+] (1 0 0), 420 [M+] (10). Anal. Calcd for C17H25N4NaO5S (420.14): C, 48.57; H, 5.95. Found: C, 48.30; H, 6.18. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 1-phenyl-1H-tetrazole-5-thiol With cesium hydroxide In methanol at 20℃; for 2h; Stage #2: 15-crown-5 In methanol for 5h; | 5 2.2.1 [Li(15-crown-5)(SCN4Ph)] (2) General procedure: LiOH (0.068 g, 2.81 mmol) was added to a solution of 1-phenyl-1-H-tetrazole-5-thione (1) (0.50 g, 2.81 mmol) in methanol (40 mL) at ambient temperature. The solution was stirred for 2 h and then 15-crown-5 ether (1,4,7,10,13-Pentaoxacyclopentadecane) (0.62 g, 2.81 mmol) was added. The reaction mixture was stirred for 5 h and the volume of the solution was reduced and allowed to crystallize. Yield: 88%. 2.2.5 [Cs(15-crown-5)2][SCN4Ph] (6) Compound 6 was prepared using the same procedure outlined for 2 starting from 1 (0.25 g, 1.40 mmol), CsOH (0.21 g, 1.40 mmol) and 15-crown-5 ether (0.62 g, 2.80 mmol). Yield: 76% (0.80 g, 1.49 mmol). Mp: 148-150 °C (dec). IR (KBr): 2941, 2903, 2865, 1640, 1592, 1493, 1121 (C-O) cm-1. 1H NMR (300 MHz, CDCl3, 25 °C): δ 3.59 (m, 40H, CH2-O), 7.27 (t, 1H, p-ArH), 7.40 (t, 2H, m-ArH), 8.06 (d, 2H, o-ArH) ppm. 13C NMR (75 MHz. CDCl3, 25 °C): δ 69.4 (C-O), 124.2 (o-C), 127.3 (p-C), 128.5 (m-C), 137.2 (i-C), 167.5 (CS) ppm. FAB+ m/z (%): 353 [Cs(15-crown-5)+] (1 0 0), 573 [Cs(15-crown-5)2+] (12). Anal. Calcd for C27H45CsN4O10S (750.19): C, 43.20; H, 6.00. Found: C, 42.89; H, 6.04. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | A 200ml Schlenk flask with a stirrer and reflux condenser was purged with argon and charged with metallic calcium (pieces 0.86g, 21.5mmol), 15-crown-5 (4.73g, 21.5mmol), absolute ethanol (100cm3) and the mixture was heated under stirring and reflux until the calcium was completely dissolved, then Hfod (12.7g, 43.0mmol) was added in course of 1h. Ethanol was removed from reaction mixture completely under vacuum pumping; the white powder, that formed, was dried in dynamic vacuum at 80C and dissolved in hot n-hexane. The hexane solution was filtered and cooled at 0C for 24h. The obtained precipitate was recrystallized from n-hexane and dried in dynamic vacuum at 90C for 1h. Recrystallization from dichloromethane-hexane solution and storage in course of 6days at 0C afforded colorless crystals suitable for X-ray investigation. Yield 14.9g, 80%. M.p.110C. Anal. Calc. for C30H40O9F14Ca: C, 42.36; H, 4.73. Found: C, 42.61; H,4.78.IR(cm-1 Nujol mulls): 1650s, 1641s, 1529sh, 1513s, 1502s, 1464s, 1379s, 1284sh, 1224s, 1180s, 1163m, 1136m, 1101s, 958m, 906m, 833m, 750m, 621w, 530w, 470w. 1H NMR (CDCl3, 200MHz, 27C) δ ppm: 1.04 (s, 18H, C(CH3)3 of fod), 3.76 (s, 20H, CH2 of 15-crown-5), 5.63 (s, 2H, CH of fod). 19F NMR (CDCl3, 376MHz, 25C) δ ppm: -80.81 (t, J=9.0Hz, 3F, CF3), -119.5 (m, 2F, CF3CF2CF2), -126.7 (m, 2F, CF3CF2CF2). 13C NMR (CDCl3, 100MHz, 25C) δ ppm: 27.7 (m, C(CH3)3), 41.3 (s, C(CH3)3), 68.9(s, OCH2 of 15-crown-5), 90.3 (m, CH of fod), 109.0(t.sext,1J=260Hz,2J=37Hz, CF3CF2CF2), 111.0 (t.t, 1J=260Hz, 2J=30Hz, CF3CF2CF2), 118.1(q.t. 1J=288Hz, 2J=35Hz, CF3CF2CF2), 169.8(t, J=21Hz, C3F7CO of fod), 203.4 (s, (CH3)3CCO of fod). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | The experiment was carried out after the sample of metallic calcium was kept at moist atmosphere in the course of the week. The obtained composite was metallic calcium covered by surface calcium hydroxide. Percentage of metallic calcium (36%) in composite was established by volumetric method. The sample of composite, containing metallic calcium (0.16g, 4mmol), Ca(OH)2 (0.28g, 4mmol) and 15-crown-5 (2.42g, 11mmol) were heated in 100cm3 of toluene at reflux, then Hfod (2.73g, 44mmol) was added dropwise to reaction mixture at refluxing in the course of 3h. Almost of all composite was dissolved during this time giving a clear solution. The resulting solution was cooled to room temperature to give the colorless precipitate. The obtained precipitate was collected on a glass filter. Recrystallization from toluene and draining in dynamic vacuum at 80C for 2h produced white microcrystalline solid product, which was analyzed by elemental analyses, IR, 1H NMR, 13C NMR, and 19F NMR spectroscopy and shown to be complex 2. Yield 5.67g, (60%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With nitrosyl hexafluorophosphate; calcium In acetonitrile at 20℃; for 72h; Inert atmosphere; | 1 Example 1 - Synthesis of (Cacl5-crown-5)(PF6)2 In a Schlenk flask, Ca (>95% purchased from Sigma Aldrich) was suspended in freshly distilled CH3CN along with 15-crown-S (Sigma Aldrich) and stirred at room temperature under a nitrogen atmosphere. In a separate Schlenk flask, NOPF6 (purchased from ACROS Organics) was dissolved in freshly distilled CH3CN under a nitrogen atmosphere. The NOPF6 solution was then added slowly to the Ca granules using a dry syringe. The reaction mixture was stirred at room temperature for ca. 3 days. The off-white solution was then filtered through a cannula using a glass fibre filter and dried in vacuo. The resulting solid was dissolved in a minimum amount of dry CH3CN, layered with dry Et20, and left undisturbed for several days during which colourless crystals formed. The supernatant was then decanted to isolate the colourless crystals of(CaclScrown-5)(PF 6)2 in 46% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With sodium methylate In methanol at 20℃; for 3h; Inert atmosphere; Schlenk technique; | 2. Synthesis of sodium or potassium bis(catecholato)-alkyl silicate General procedure: All manipulations were performed following the conventional Schlenk techniques. In a dry Schlenk tube under argon covered with aluminium fold was added catechol (2 equiv) and the Schlenkwas purged. Degassed MeOH (0.25 M) was added followed by the alkyltriethoxysilane (1 equiv.). A solutionof sodium or potassium methoxide in methanol (1 equiv) was added dropwise and the reaction was stirred 3hours at room temperature. Solvent was removed directly on the Schlenk line and the crude was dry underhigh vacuum until a powder was obtained. Silicate was purified by recrystallisation as mentioned for eachsilicate. The crystals were collected by filtration under argon flux, washed with degassed diethyl ether anddried under vacuum to afford the desired silicate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In N,N-dimethyl-formamide at 20℃; for 1h; | Synthesis of [Ag(C10H20O5)(NO3)] (1) A solution of AgNO3 (0.100 g, 0.592 mmol) in 3 mL of DMF was addedwith 15-crown-5 (0.130 g, 0.591 mmol). The reaction mixture was stirred for 1 h at room temperature and then placed intodiethyl ether vapor at 5 °C. In a few days, colorless crystals of the product were isolated, washed with Et2O, and dried in theair. The complex is stable in the air, but unstable in the light. When exposed to light, the silver formation is visually observed.Yield: 0.173 g (75%). IR (ATR, cm-1): 1475 w, 1399 m, 1352 m, 1294 s, 1252 m, 1108 s, 1090 vs, 1047 m, 1031 s, 940 s,852 w, 822 m, 801 w. Calculated for [Ag(C10H20O5)(NO3)] C, H, N (%): 30.8, 5.2, 3.6. Found C, H, N (%): 30.5, 5.0, 3.9 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97.74% | Stage #1: iron(II) bis(trimethylsilyl)amide; sodium hexamethyldisilazane In toluene for 1h; Reflux; Inert atmosphere; Glovebox; Schlenk technique; Stage #2: 15-crown-5 In toluene for 1h; Reflux; Inert atmosphere; Glovebox; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium hydrogen sulfide In methanol at 20℃; for 0.5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.9% | In tetrahydrofuran at -35℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | Stage #1: 15-crown-5 With sodium metabisulfite In water; acetonitrile at 20℃; Irradiation; Stage #2: allyl bromide at 60℃; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: phenanthrene With potassium In tetrahydrofuran Inert atmosphere; Stage #2: 15-crown-5 In tetrahydrofuran for 1h; Inert atmosphere; | Synthesis of K(15c5)2Phen and K(18c6)Phen: General procedure: Freshly cut potassium(14.4 mmol) and phenanthrene (14.3 mmol) were dissolved inTHF overnight. The solution turned to a dark green color. Dried15-crown-5 or 18-crown-6 (28.8 mmol) was added to the reactionmixture under stirring. The dark potassium crown ether phenanthrenidesalt was formed within an hour. After washing the salt with(cold) THF, it was dried under vacuum (10-3 mbar) for at least 12 h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44.4% | With potassium In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30.8% | With sodium In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; |
Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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