53914-95-7

Basic information

• Product Name: BIS(1,4-PHENYLENE)-34-CROWN 10-ETHER
• Synonyms: BIS(1,4-PHENYLENE)-34-CROWN 10-ETHER
• CAS NO: 53914-95-7
• Molecular Formula: C₂₈H₄₀O₁₀
• Molecular Weight: 644.79208
• Product Categories: Crown Ethers;Functional Materials;Macrocycles for Host-Guest Chemistry
• Mol File: 53914-95-7.mol
• Article Data: 11

Chemical Properties

• Melting Point: 69.0 ~73.0 °C
• Boiling Point: 689.9°C at 760 mmHg
• Flash Point: 267.2°C
• Appearance: /
• Density: 1.068g/cm³
• Vapor Pressure: 4.23E-18mmHg at 25°C
• Refractive Index: 1.465
• CAS DataBase Reference: BIS(1,4-PHENYLENE)-34-CROWN 10-ETHER(CAS DataBase Reference)
• NIST Chemistry Reference: BIS(1,4-PHENYLENE)-34-CROWN 10-ETHER(53914-95-7)
• EPA Substance Registry System: BIS(1,4-PHENYLENE)-34-CROWN 10-ETHER(53914-95-7)

Safety Data

• Hazardous Substances Data: 53914-95-7(Hazardous Substances Data)

Usage

General Description

Bis(1,4-phenylene)-34-crown 10-ether is a synthetic, organic compound classified as a crown ether. Crown ethers are cyclic chemical compounds that consist of a ring of organic molecules, usually in the shape of a crown. They are polyether composites of either ethylene oxide or propylene oxide subunits. As is common to all crown ethers, bis(1,4-phenylene)-34-crown 10-ether is known for its ability to bind with certain metal cations, giving it potential use in various chemical applications. Further studies are required to understand its properties, stability and potential risks.

InChI:InChI=1/C28H40O10/c1-2-26-4-3-25(1)35-21-17-31-13-9-29-11-15-33-19-23-37-27-5-7-28(8-6-27)38-24-20-34-16-12-30-10-14-32-18-22-36-26/h1-8H,9-24H2

Synthetic route

tetraethylene glycol di(p-toluenesulfonate) (37860-51-8) + 1,11-bis<4-hydroxyphenoxy>-3,6,9-trioxaundecane (14556-10-6) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
With sodium hydride In tetrahydrofuran for 120h; Heating;	25%
With tetra-(n-butyl)ammonium iodide; caesium carbonate; cesium 4-methylbenzenesulfonate 1.) DMF, 80 deg C, 1.5 h, 2.) DMF, 100 deg C, 4 d; Yield given. Multistep reaction;

1,4-bis[2-(2-(2-(2-toluene-p-sulfonylethoxy)ethoxy)ethoxy)ethoxy]benzene (134881-77-9) + hydroquinone (123-31-9) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
With potassium carbonate In acetone for 48h; Heating;	25%
With caesium carbonate for 72h; Cyclization; Heating;	15%

1-bromo-2-{2-[2-(2-bromoethoxy)ethoxy]-ethoxy}ethane (31255-26-2) + 1,11-bis<4-hydroxyphenoxy>-3,6,9-trioxaundecane (14556-10-6) → bis(p-phenylene)[34]crown-10 (53914-95-7) + 1,4,7,10,13,18,21,24,27,30,35,38,41,44,47,52,55,58,61,64-icosaoxa<13,13,13,13>tetraparacyclophane (134940-41-3)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 80℃; for 48h;	A 18% B 0.23%

tetraethylene glycol di(p-toluenesulfonate) (37860-51-8) + hydroquinone (123-31-9) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Stage #1: hydroquinone With sodium hydroxide In water; butan-1-ol for 0.5h; Reflux; Inert atmosphere; Stage #2: tetraethylene glycol di(p-toluenesulfonate) With caesium carbonate In 1,4-dioxane; butan-1-ol for 20h; Reflux;	12.8%
With sodium hydroxide In isopropyl alcohol for 24h; Heating;	150 mg

tetraethylene glycol di(p-toluenesulfonate) (37860-51-8) + 1,11-bis<4-(benzyloxy)phenoxy>-3,6,9-trioxaundecane (113816-32-3) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
With palladium on activated charcoal; hydrogen; sodium hydride 1.) MeOH, Et2O, 2.) Me2NCHO, 70 deg C, 24 h; Yield given. Multistep reaction;

1,4-bis[2-(2-hydroxyethoxy)ethoxy]benzene bis(4-methylbenzenesulfonate) (135974-61-7) + 1,4-bis[2-(2-hydroxyethoxy)ethoxy]benzene (35648-87-4) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
With sodium hydride 1.) THF, 1 h, 2.) THF, reflux 4 d; Yield given. Multistep reaction;

C98H106N2O6(2+)*C28H40O10*2F6P(1-) → bis(p-phenylene)[34]crown-10 (53914-95-7) + C98H106N2O6(2+)*2F6P(1-)

Conditions	Yield
In dimethylsulfoxide-d6 at 100℃; Rate constant;

C28H40O10*C12H14N2(2+)*2F6P(1-) (113816-15-2) → bis(p-phenylene)[34]crown-10 (53914-95-7) + N,N'-dimethyl-4,4'-bipyridinium dihexafluorophosphate (67994-95-0)

Conditions	Yield
In acetone at 25℃; Equilibrium constant; slipping-off;

1,1'-bis(4-(2-(2-(4-[bis{4-tert-butylphenyl}-4-ethylphenylmethyl]phenoxy)ethoxy)ethoxy)benzyl)-4,4'-bipyridinium bis-p-phenylene-34-crown-10-bis(hexafluorophosphate) → bis(p-phenylene)[34]crown-10 (53914-95-7) + 1,1'-bis(4-(2-(2-(4-[bis{tert-butylphenyl}-4-ethylphenylmethyl]phenoxy)ethoxy)ethoxy)benzyl)-4,4'-bipyridinium bis(hexafluorophosphate)

Conditions	Yield
In [D3]acetonitrile at 50℃; Activation energy; slipping-off;

tetraethylene glycol di(p-toluenesulfonate) (37860-51-8) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / K2CO3 / acetone / 48 h / Heating 2: 25 percent / K2CO3 / acetone / 48 h / Heating View Scheme
Multi-step reaction with 2 steps 1: 68 percent / NaH / dimethylformamide / 24 h / 80 °C 2: 1.) H2, Pd/C, 2.) NaH / 1.) MeOH, Et2O, 2.) Me2NCHO, 70 deg C, 24 h View Scheme
Multi-step reaction with 3 steps 1: 1.) NaH / 1.) DMF, 15 min, 2.) DMF, 80 deg C, 24 h 2: 99 percent / H2 / 10percent Pd/C / methanol; CHCl3 3: 25 percent / NaH / tetrahydrofuran / 120 h / Heating View Scheme

hydroquinone (123-31-9) + K2CO3 → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / K2CO3 / acetone / 48 h / Heating 2: 25 percent / K2CO3 / acetone / 48 h / Heating View Scheme

4-Benzyloxyphenol (103-16-2) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 68 percent / NaH / dimethylformamide / 24 h / 80 °C 2: 1.) H2, Pd/C, 2.) NaH / 1.) MeOH, Et2O, 2.) Me2NCHO, 70 deg C, 24 h View Scheme
Multi-step reaction with 3 steps 1: 1.) NaH / 1.) DMF, 15 min, 2.) DMF, 80 deg C, 24 h 2: 99 percent / H2 / 10percent Pd/C / methanol; CHCl3 3: 25 percent / NaH / tetrahydrofuran / 120 h / Heating View Scheme

hydroquinone (123-31-9) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: 63 percent / K2CO3 / dimethylformamide / 18 h / Ambient temperature 2: 68 percent / NaH / dimethylformamide / 24 h / 80 °C 3: 1.) H2, Pd/C, 2.) NaH / 1.) MeOH, Et2O, 2.) Me2NCHO, 70 deg C, 24 h View Scheme
Multi-step reaction with 2 steps 1: 1.) K2CO3 / 1.) DMF, 30 min, 2.) DMF, 75 deg C, 7 d 2: 1.) NaH / 1.) THF, 1 h, 2.) THF, reflux 4 d View Scheme
Multi-step reaction with 3 steps 1: 1.) K2CO3 / 1.) DMF, 30 min, 2.) DMF, 75 deg C, 7 d 2: 88 percent / triethylamine / CH2Cl2 / 15 h / Ambient temperature 3: 1.) NaH / 1.) THF, 1 h, 2.) THF, reflux 4 d View Scheme

1,11-bis<4-(benzyloxy)phenoxy>-3,6,9-trioxaundecane (113816-32-3) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 99 percent / H2 / 10percent Pd/C / methanol; CHCl3 2: 25 percent / NaH / tetrahydrofuran / 120 h / Heating View Scheme

1,4-bis[2-(2-hydroxyethoxy)ethoxy]benzene (35648-87-4) → bis(p-phenylene)[34]crown-10 (53914-95-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 88 percent / triethylamine / CH2Cl2 / 15 h / Ambient temperature 2: 1.) NaH / 1.) THF, 1 h, 2.) THF, reflux 4 d View Scheme

2C2F3O2(1-)*C13H13N5(2+)*C28H40O10 → bis(p-phenylene)[34]crown-10 (53914-95-7) + C13H11N5

Conditions	Yield
With N-ethyl-N,N-diisopropylamine

bis(p-phenylene)[34]crown-10 (53914-95-7) + acetone (67-64-1) + (E)-bis(4-benzylaminomethyl)stilbene bis(hexafluorophosphate) → C30H30N2*C28H40O10*2C3H6O*2F6P(1-)*2H(1+)

Conditions	Yield
In dichloromethane	90%

bis(p-phenylene)[34]crown-10 (53914-95-7) + N,N'-bis[3-(carboethoxy)propyl]-4,4'-bipyridinium hexafluorophosphate → C22H30N2O4(2+)*C28H40O10*2F6P(1-)

Conditions	Yield
In methanol; acetone at 20℃;	90%

(C5H4N)5CH2CH2C6H4CH2(3+)*3NO3(1-)=(C5H4N)5CH2CH2C6H4CH2(NO3)3 + ammonium hexafluorophosphate + bis(p-phenylene)[34]crown-10 (53914-95-7) + dinitrato(1,2-diaminoethane)platinum(II) → Pt(NH2C2H4NH2)(C5H4N)5CH2CH2C6H4CH2(5+)*(C6H4)2C16H32O10*5PF6(1-)=Pt(N2H4C2H4)(C5H4N)5C3H6C6H4(PF6)5*(C6H4)2C16H32O10

Conditions	Yield
In water equimolar soln. of bipyridyl-compound, Pd-complex and macrocycle in H2O was heated at 100°C for 12 d, NH4PF6 was added;	85%

4-[2-(2-{4-[bis-(4-tert-butyl-phenyl)-phenyl-methyl]-phenoxy}-ethoxy)-ethoxy]-pyridine + C62H65BrN2O3(2+)*2F6P(1-) + bis(p-phenylene)[34]crown-10 (53914-95-7) → TIMEOUT: 5s + C104H112N3O6(3+)*C28H40O10*3F6P(1-)

Conditions	Yield
Stage #1: 4-[2-(2-{4-[bis-(4-tert-butyl-phenyl)-phenyl-methyl]-phenoxy}-ethoxy)-ethoxy]-pyridine; C62H65BrN2O3(2+)*2F6P(1-); bis(p-phenylene)[34]crown-10 at 20℃; for 4.08333h; Air atmosphere; Neat (no solvent); Stage #2: With ammonium hexafluorophosphate In chloroform; water; acetone	A 8% B 85%

bis(p-phenylene)[34]crown-10 (53914-95-7) + cyclobis(paraquat-4,4’-biphenylene) hexafluorophosphate → C48H40N4(4+)*2C28H40O10*4F6P(1-) (134815-81-9)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In [D3]acetonitrile at 80℃; for 72h;	84%

C74H82N4O4(2+)*2Br(1-) + 1,4-bis(bromomethyl)benzene (623-24-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) → C82H90N4O4(4+)*C28H40O10*4Br(1-)

Conditions	Yield
In N,N-dimethyl-formamide	80%

bis(p-phenylene)[34]crown-10 (53914-95-7) + 4-[2-[2-[4-[4-ethylphenyl-bis{4-t-butylphenyl}methyl]phenoxy]ethoxy]ethoxy]benzylbromide (544708-59-0) + 1-{4-[tris{4-(4-phosphonodiethoxyphenyl)phenyl}methyl]phenyl}-1'-(3-[3,3'-dimethyl-4,4'-bipyridyl-1-yl]propyl)-4,4'-bipyridinium tris(hexafluorophosphate) → C126H137N4O12P3(4+)*C28H40O10*4F6P(1-)

Conditions	Yield
In benzonitrile at 20℃; for 144h;	75%

1,4-bis(bromomethyl)benzene (623-24-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) + 1,1-[1,4-phenylenebis(methylene)]bis-4,4'-pyridylpiridinium bis(hexafluorophosphate) (108861-20-7) → <2>---catenane tetrakis(hexafluorophosphate) (122801-13-2)

Conditions	Yield
With ammonium hexafluorophosphate In N,N-dimethyl-formamide under 7500600 Torr; Ambient temperature;	74%
With ammonium hexafluorophosphate at 20℃; catenation;	70%
In N,N-dimethyl-formamide at 80℃; for 1h;	34%

bis(p-phenylene)[34]crown-10 (53914-95-7) + [Pt2(1,1'-methylenebis-4,4'-bipyridinium)2(en)2](hexafluorophosphate)4(OTf)4 → [Pd2(1,1'-methylenebis-4,4'-bipyridinium)2(en)2](hexafluorophosphate)8*2BPP34C10

Conditions	Yield
In acetonitrile heating soln. of platinum compd. and cyclophane deriv. in acetonitrile at 50°C for 7 d; cooling to room temp, filtration, addn. of water and amberlite CG-400, sirring for 24 h at room temp., filtration, addn. of KPF6, filtration, elem. anal.;	70%

C46H52O4 + 4,4'-bipyridine (553-26-4) + 4-bromo-1-(2-tetrahydropyranyloxy)butane (31608-22-7) + bis(p-phenylene)[34]crown-10 (53914-95-7) + α,α'-dibromo-p-xylene → C82H90N4O4(4+)*C28H40O10*4Br(1-)

Conditions	Yield
Multistep reaction;	66%

C44H49BrO3 + C54H57N2O3(1+)*F6P(1-) + bis(p-phenylene)[34]crown-10 (53914-95-7) → C98H106N2O6(2+)*2F6P(1-) + C98H106N2O6(2+)*C28H40O10*2F6P(1-)

Conditions	Yield
Stage #1: C44H49BrO3; C54H57N2O3(1+)*F6P(1-); bis(p-phenylene)[34]crown-10 at 20℃; for 2.08333h; Air atmosphere; Neat (no solvent); Stage #2: With ammonium hexafluorophosphate In chloroform; water; acetone	A 20% B 64%

bis(p-phenylene)[34]crown-10 (53914-95-7) + trans-1,2-bis(pyridin-4-yl)ethene (13362-78-2) + benzene-1,2-diol (120-80-9) + toluene (108-88-3) + 3,5-bis-trifluromethylphenylboronic acid (73852-19-4) → (C6H4O(CH2CH2O)4)2*(CHC5H4NB(C6H4O2)C6H3(CF3)2)2*3C7H8

Conditions	Yield
In toluene DPE, catechol, B compd., and crown (1:2:2:1) heated; cooled to room temp., septd., NMR;	63%

bis(p-phenylene)[34]crown-10 (53914-95-7) + benzene-1,2-diol (120-80-9) + 3,5-bis-trifluromethylphenylboronic acid (73852-19-4) + trans-1,2-bis(4-pyridyl)ethylene (1135-32-6) → C28H40O10*C40H24B2F12N2O4 (1061570-77-1)

Conditions	Yield
In benzene for 1h; Reflux; Inert atmosphere;	63%

C76H86N4O4(2+)*2Br(1-) + 1,4-bis(bromomethyl)benzene (623-24-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) → C84H94N4O4(4+)*C28H40O10*4Br(1-)

Conditions	Yield
In N,N-dimethyl-formamide	61%

bis(p-phenylene)[34]crown-10 (53914-95-7) + 1,1''-(1,3-phenylene-bis(methylene))bis-4,4'-bipyridinium-bis(hexafluorophosphate) (108861-18-3) + 1,3-bis-(bromomethyl)benzene (626-15-3) → <<2>-<1,4,7,10,13,20,23,26,29,32-decaoxa<13.13>paracyclophane><9,18,29,38-tetraazonia<1.1.0>para<1>meta<1.0>paracyclophane>catenane> tetrakishexafluorophosphate

Conditions	Yield
With ammonium hexafluorophosphate In N,N-dimethyl-formamide under 7500600 Torr; for 7h; Ambient temperature;	59%

1-{4-[tris(4-t-butylphenyl)-methyl]-phenyl}-4,4'-bipyridinium hexafluorophosphate (1020666-50-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) + 4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzylbromide (544708-54-5) → 1-{4-[tris(4-t-butylphenyl)-methyl]-phenyl}-(4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzyl)[4,4']-bipyridinium bis-hexafluorophosphate + C28H40O10*C95H108N2O3(2+)*2F6P(1-)

Conditions	Yield
In benzonitrile at 20℃; for 120h;	A 37% B 56%

1,4-bis(bromomethyl)benzene (623-24-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) + 25,27-bis[3-(4,4'-bipyridine-1'-yl)propoxy]-26,28-dihydroxycalix[4]arene dichloride → [25,27-dihydroxy-26,28-{3-[p-xylylbis[4-(4,4'-bipyridine-1'-yl)]propoxy]}calix[4]arene (cone) tetrachloride]-[1,4,7,10,17,20,23,26,28,32-decaoxa[13.13]paracyclophane][2]catenane

Conditions	Yield
With ammonium chloride In N,N-dimethyl-formamide at 25℃; for 336h; Substitution;	53%

bis(p-phenylene)[34]crown-10 (53914-95-7) + C98H106N2O6(2+)*2F6P(1-) → C98H106N2O6(2+)*C28H40O10*2F6P(1-)

Conditions	Yield
In acetonitrile at 55℃; for 240h;	52%
In acetonitrile at 24.9℃; Kinetics; var. temp.;

bis(p-phenylene)[34]crown-10 (53914-95-7) + C117H124N4O7(4+)*4F6P(1-) → C117H124N4O7(4+)*2C28H40O10*4F6P(1-) + C117H124N4O7(4+)*C28H40O10*4F6P(1-)

Conditions	Yield
In tetrahydrofuran at 55℃; for 240h; rotaxane formation;	A 52% B 14%

potassium hexafluorophosphate (17084-13-8) + bis(p-phenylene)[34]crown-10 (53914-95-7) + (ethylenediamine)Pt(OTf)2 (960068-70-6) + 1-(4-(pyridin-4-yl)benzyl)-4,4'-bipyridin-1-ium nitrate (1141448-00-1) → (Pt2(N2C10H8CH2C11H8N)2(NH2C2H4NH2)2)(6+)*6PF6(1-)*C28H40O10=(Pt2(N2C10H8CH2C6H4C5H4N)2(NH2C2H4NH2)2)(PF6)6*C28H40O10

Conditions

Yield

In acetonitrile soln. Pt complex, ligand and polyether in MeCN was heated at 55°Cfor 8 days, cooled to room temp., Et2O was added, ppt. was filtered, su spnd. in water, Amberlite IRA-402 was added, stirred for 24 h; soln. was filtered and evapd. in vacuo, column chromy. on silica (acetone - 1.5M NH4Cl - MeOH 5:4:1), solvent was removed in vacuo, residue was dissolved in water, KPF6 was added, ppt. was filtered and washed with water; elem. anal.;

52%

1,4-bis(bromomethyl)benzene (623-24-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) + 25,27-bis[3-(4,4'-bipyridine-1'-yl)propoxy]-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene dihexafluorophosphate → [25,27-dihydroxy-5,11,17,23-tetra(tert-butyl)-26,28-{3-[p-xylylbis[4-(4,4'-bipyridine-1'-yl)]propoxy]}calix[4]arene (cone) tetra(hexafluorophosphate)]-[1,4,7,10,17,20,23,26,28,32-decaoxa[13.13]paracyclophane][2]catenane

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 240h; Substitution;	51%
In acetonitrile for 168h; Ambient temperature;	35%

C72H78N4O4(2+)*2Br(1-) + 1,4-bis(bromomethyl)benzene (623-24-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) → C80H86N4O4(4+)*C28H40O10*4Br(1-)

Conditions	Yield
In N,N-dimethyl-formamide	51%

1-{4-[tris(4-t-butylphenyl)-methyl]-phenyl}-4,4'-bipyridinium hexafluorophosphate (1020666-50-5) + bis(p-phenylene)[34]crown-10 (53914-95-7) + 4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzylbromide (544708-54-5) → 1-{4-[tris(4-t-butylphenyl)-methyl]phenyl}-1'-(4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzyl)-[4,4']-bipyridinium bis-p-phenylene-34-crown-10-12,152-disulphonate (1030850-41-9) + 1-{4-[tris(4-t-butylphenyl)-methyl]phenyl}-(4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzyl)-[4,4']-bipyridinium bis-p-phenylene-34-crown-10-12,153-disulphonate

Conditions	Yield
Stage #1: bis(p-phenylene)[34]crown-10 With chlorosulfonic acid at 0℃; for 1h; Stage #2: With tetramethyl ammoniumhydroxide In methanol for 2h; Stage #3: 1-{4-[tris(4-t-butylphenyl)-methyl]-phenyl}-4,4'-bipyridinium hexafluorophosphate; 4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzylbromide In acetonitrile at 20℃; for 144h; Further stages.;	A 50% B 50%

bis(p-phenylene)[34]crown-10 (53914-95-7) + (N,N’)-diethyl-4,4’-bipyridinium dihexafluorophosphate (138926-07-5) → 1,1'-diethyl-[4,4']-bipyridinium bis-p-phenylene-34-crown-10-12,152-disulphonate sesquiethanolate (1030850-36-2)

Conditions	Yield
Stage #1: bis(p-phenylene)[34]crown-10 With chlorosulfonic acid at 0℃; for 1h; Stage #2: With tetramethyl ammoniumhydroxide In methanol for 2h; Stage #3: (N,N’)-diethyl-4,4’-bipyridinium dihexafluorophosphate In methanol; ethanol Further stages.;	50%

bis(p-phenylene)[34]crown-10 (53914-95-7) + 1,1''-(1,3-phenylene-bis(methylene))bis-4,4'-bipyridinium-bis(hexafluorophosphate) (108861-18-3) + 3,3'-bis(α-bromomethyl)azobenzene (93824-64-7) → C42H36N6(4+)*C28H40O10*4F6P(1-)

Conditions	Yield
With ammonium hexafluorophosphate; nitromethane; tetraethylammonium chloride; water In acetonitrile for 192h; Ambient temperature;	49%

bis(p-phenylene)[34]crown-10 (53914-95-7) + 4-(2-(2-(4-[tris-{4-t-butylphenyl}-methyl]-phenoxy)-ethoxy)-ethoxy)-benzylbromide (544708-54-5) + 1-{4-[tris{4-(4-(diethylphosphono)phenyl)-phenyl}-methyl]-phenyl}-4-(4'pyridyl)-pyridinium hexafluorophosphate → 1-{4-[tris{4-(4-phosphonodiethoxyphenyl)phenyl}methyl]phenyl}-(4-(2-(2-(4-[tris{4-t-butylphenyl}methyl]phenoxy)ethoxy)ethoxy)benzyl)-4,4'-bipyridinium bis(hexafluorophosphate) + 1-{4-[tris{4-(4-phosphonodiethoxyphenyl)phenyl}methyl]phenyl}-(4-(2-(2-(4-[tris{4-t-butylphenyl}methyl]phenoxy)ethoxy)ethoxy)benzyl)-4,4'-bipyridinium*bis-para-phenylene-34-crown-10 [2]rotaxane bis(hexafluorophosphate)

Conditions	Yield
In benzonitrile at 20℃; for 120h;	A 36% B 48%

bis(p-phenylene)[34]crown-10 (53914-95-7) + 1,1'-bis(4-(2-(2-(4-[bis{tert-butylphenyl}-4-ethylphenylmethyl]phenoxy)ethoxy)ethoxy)benzyl)-4,4'-bipyridinium bis(hexafluorophosphate) → 1,1'-bis(4-(2-(2-(4-[bis{4-tert-butylphenyl}-4-ethylphenylmethyl]phenoxy)ethoxy)ethoxy)benzyl)-4,4'-bipyridinium bis-p-phenylene-34-crown-10-bis(hexafluorophosphate)

Conditions	Yield
In acetonitrile at 55℃; for 240h;	47%
In acetonitrile at 29.9℃; Kinetics; var. temp.;

bis(p-phenylene)[34]crown-10 (53914-95-7) + C174H186N6O9(6+)*6F6P(1-) → C174H186N6O9(6+)*2C28H40O10*6F6P(1-) + C174H186N6O9(6+)*C28H40O10*6F6P(1-) + C174H186N6O9(6+)*3C28H40O10*6F6P(1-)

Conditions	Yield
In acetonitrile at 50℃; for 240h;	A 26% B 46% C 6%
In acetonitrile at 50℃; for 240h;	A 41% B 19% C 22%

bis(p-phenylene)[34]crown-10 (53914-95-7) + C100H110N2O6(2+)*2F6P(1-) → C100H110N2O6(2+)*C28H40O10*2F6P(1-)

Conditions	Yield
In acetonitrile at 55℃; for 240h;	45%
In acetonitrile at 24.9℃; Kinetics; var. temp.;

bis(p-phenylene)[34]crown-10 (53914-95-7) + trans-1,2-bis(pyridin-4-yl)ethene (13362-78-2) + 1,1'-bis(4-(bromomethyl)benzyl)-4,4'-bipyridine-1,1'-diium bis(hexafluorophosphate) → <<2>-<1,4,7,10,17,20,23,26,29,32-decaoxa<13.13>paracyclophane><(E)-6,17,26,37-tetraazonia<2.1.1.0.1.1>paracyclo-1-phene>catenane> tetrakis(hexafluorophospate)

Conditions	Yield
With ammonium hexafluorophosphate In N,N-dimethyl-formamide for 360h; Ambient temperature;	43%
With ammonium hexafluorophosphate In acetonitrile for 120h; Ambient temperature;	23%

Upstream product

• 31255-26-2 1-bromo-2-{2-[2-(2-bromoethoxy)ethoxy]-ethoxy}ethane 
• 14556-10-6 1,11-bis<4-hydroxyphenoxy>-3,6,9-trioxaundecane 
• 35648-87-4 1,4-bis[2-(2-hydroxyethoxy)ethoxy]benzene 
• 113816-32-3 1,11-bis<4-(benzyloxy)phenoxy>-3,6,9-trioxaundecane 
• 123-31-9 hydroquinone 
• 103-16-2 4-Benzyloxyphenol 
• 37860-51-8 tetraethylene glycol di(p-toluenesulfonate) 
• 113816-15-2 C₂₈H₄₀O₁₀*C₁₂H₁₄N₂⁽²⁺⁾*2F₆P^(1-) 
• 134881-77-9 1,4-bis[2-(2-(2-(2-toluene-p-sulfonylethoxy)ethoxy)ethoxy)ethoxy]benzene 
• 135974-61-7 1,4-bis[2-(2-hydroxyethoxy)ethoxy]benzene bis(4-methylbenzenesulfonate) 

Downstream Products

• 144205-60-7 C₁₂₄H₁₃₈N₄O₆⁽⁴⁺⁾*C₂₈H₄₀O₁₀*4F₆P^(1-) 
• 1061570-77-1 C₂₈H₄₀O₁₀*C₄₀H₂₄B₂F₁₂N₂O₄ 

Relevant articles and documents

Conformational interconversions in [2]catenanes containing a wide rigid bis(p-benzyl)methyl spacer

(Figure Presented) The conformational interconversions of four [2]catenanes (1-4) containing a dibenzo-34-crown-10 ether (BPP34C10) interlocked with rings containing two 4,4′-dipyridiniums tethered by 1,3-bis(ethyloxy)-phenyl and bis(p-benzyl)methyl spacers have been studied by VT 1H NMR spectroscopy. Symmetrically placed blocking groups on thickened tethers enabled either pathway for circumrotation of the BPP34C10 between isoenergetic sites to be blocked. On the basis of chemical shifts of the BPP34C10, its internal p-hydroquinone forms π-π-stacking interactions with only one 4,4′-dipyridinium ring at a time. The activation barrier for migration along either open tether was approximately 11.5 kcal/mol. This study demonstrates an ability to select the pathway for conformational interconversions in these [2]catenanes containing the rigid bis(p-benzyl)methyl tether and the lowering the barrier for interconversion through destabilization of the ground state structures.

From p-dimethoxybenzene to crown-benzenophanes, 4: Cation-complexing properties of Bis(p-phenylene-34-crown-10) - A structural and spectrophotometric study

The title compound 2, an electron-rich macrocyclic paracyclophane of the coronand type, known to form a charge-transfer complex with paraquat, was found to encapsulate strontium cations and to bind to magnesium cations. X-ray analysis revealed that 2 forms a 2:1 (metal/substrate) complex with Sr(ClO4)2, in which the two benzene rings weakly overlap, whereas in the single crystals grown from Mg(ClO4)2, the metal cation prefers to lie outside the coronand (1:1 stoichiometry). In acetonitrile solution, cations were observed to trigger an hypsochromic shift of the UV absorption spectra, proportional to their size and charge density. The stoichiometries and binding constants were also determined by UV absorption titration in acetonitrile using the LETAGROP-SPEFO program for several monovalent and divalent cations. For Na+, Ca2+, and Sr2+, 1:1 and 2:1 complexes were shown to be formed. In the free ligand, a weak interaction between the benzene rings was detected by fluorescence decay kinetic analysis, indicating the presence of two conformer populations within the nanosecond time scale. In solution, metal cations neither induce detectable excimer formation nor seem to have a strong influence on the fluorescence emission spectra, except a heavy atom quenching with Sr2+and Ba2+, in contrast to the effect observed in absorption. However, Sr2+ and Mg2+induce a clear hypsochromic shift in the single crystal fluorescence spectra. Compound 2 was prepared by a new and efficient route which is compared to the previous procedures. VCH Verlagsgesellschaft mbH, 1997.