20644-12-6

Basic information

• Product Name: 1,12-DICARBADODECABORANE(12)
• Synonyms: 1,12-Dicarba-closo-dodecaborane(12);1,12-Dicarbadodecaboran;p-Baren;p-Carbaboran(12);p-Carboran;p-Carboran(12);1,12-DICARBADODECABORANE(12);P-CARBORANE
• CAS NO: 20644-12-6
• Molecular Formula: C₂H₁₂B₁₀
• Molecular Weight: 144.23
• Mol File: 20644-12-6.mol
• Article Data: 4

Chemical Properties

• Melting Point: 200-203 °C(lit.)
• Appearance: /
• CAS DataBase Reference: 1,12-DICARBADODECABORANE(12)(CAS DataBase Reference)
• NIST Chemistry Reference: 1,12-DICARBADODECABORANE(12)(20644-12-6)
• EPA Substance Registry System: 1,12-DICARBADODECABORANE(12)(20644-12-6)

Safety Data

• Hazardous Substances Data: 20644-12-6(Hazardous Substances Data)

Usage

Uses

p-Carborane is used in preparation of covalent organic framework material using Carborane as starting material.

InChI:InChI=1/C2H12B10/c1-3-4(1)6(1)7(1)5(1,3)9(3)2-8(3,4,9)10(2,4,6)12(2,6,7)11(2,5,7)9/h1-12H

Synthetic route

1,2-dicarba-closo-dodecaborane(12) (16872-09-6) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With ZSM-5 zeolite at 600℃; for 3h; Temperature; Reagent/catalyst; Glovebox; Inert atmosphere;	72%
In neat (no solvent) sublimation of o-C2B10H12 at 200-250 °C, passing sublimate with N2 (heated, purified) through heated tube into cooled vessel (200 mL/min, 0.25 g o-C2B10H12/min, contact time 0.34 min, 700 °C);	22%
In neat (no solvent) thermal rearrangement at high temp.;; low yield;;

morpholine (110-91-8) + 2-iodo-closo-1,12-dodecaborane (22784-33-4) → 1,12-dicarbora-closo-dodecaborane (20644-12-6) + 2-hydroxy-1,12-dicarba-closo-dodecaborane (31726-41-7) + N-(1,12-dicarba-closo-dodecaboran-2-yl)morpholine (936951-95-0)

Conditions	Yield
With t-BuONa; Pd(dba)2; PBu(t)3*HBF4 In 1,4-dioxane under Ar atm. 2-iodo-p-carborane, carbazole, t-BuONa, Pd(dba)2 and PBu(t)3*HBF4 in dioxane were heated at 100°C for 48 h; react. mixt. was diluted with Et2O, filtered through silica, flash chromy.; elem. anal.;	A n/a B n/a C 33%
With t-BuONa; Pd(OAc)2; C6H5-o-C6H4PBu(t)2 In toluene under Ar atm. 2-iodo-p-carborane, carbazole, t-BuONa, Pd(OAc)2 andC6H5-o-C6H4PBu(t)2 in toluene were heated at 100°C for 48 h;
With t-BuONa; Pd(dba)2; BINAP In 1,4-dioxane under Ar atm. 2-iodo-p-carborane, carbazole, t-BuONa, Pd(dba)2 and BINAPin dioxane were heated at 100°C for 48 h;

1,7-dicarba-closo-dodecaborane(12) (16986-24-6) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
In neat (no solvent) izomerization of m-B2C10H12 at 615 °C (17 h);; gas chromy.;;	6.5%
In neat (no solvent) izomerization of m-B2C10H12 at 700-800 °C;; equil. with 40-50% p-C2B10H12;;
In neat (no solvent) isomerization at 650°C;;
In neat (no solvent) isomerization at 650°C;;
In neat (no solvent) isomerization at 630°C;;

nido-decaborane (17702-41-9) + acetylene (74-86-2) → 1,2-dicarba-closo-dodecaborane(12) (16872-09-6) + 1,7-dicarba-closo-dodecaborane(12) (16986-24-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
In gas gas phase react. of acetylene and B10H14;; mixt. of o-, m- and p-C2B10H12 obtained;;
In gas passing B10H14 and C2H2 (dild. with H2O) through heated tube filled with steel wool (580-800 °C, contact time with hot zone 0.5 s);; mixt. of o-, m-, and p-C2B10H12 obtained, ratio depending on temp. of react. zone (formation of o-C2B10H12 decreasing with increasing temp.);;
In neat (no solvent, gas phase) passing B10H14 and C2H2 (dild. with H2O) through heated tube filled with steel wool (580-800 °C, contact time with hot zone 0.5 s);; mixt. of o-, m-, and p-C2B10H12 obtained, ratio depending on temp. of react. zone (formation of o-C2B10H12 decreasing with increasing temp.);;
In neat (no solvent, gas phase) gas phase react. of acetylene and B10H14;; mixt. of o-, m- and p-C2B10H12 obtained;;

1,7-dicarba-closo-dodecaborane(12) (16986-24-6) → 1,2-dicarba-closo-dodecaborane(12) (16872-09-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With ammonia; sodium interconversion;
With ammonia; sodium interconversion;
With Na; NH3 interconversion;

1,2-dicarba-closo-dodecaborane(12) (16872-09-6) → 1,7-dicarba-closo-dodecaborane(12) (16986-24-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
In neat (no solvent) thermal izomerization at 620-700 °C;; 52-53% m-C2B10H12, 47-48% p-C2B10H12;;
With ammonia; sodium interconversion;
With ammonia; sodium interconversion;

1-(trimethylstannyl)-1,12-dicarba-closo-dodecaborane (51375-18-9) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With methanol; potassium hydroxide cleavage;
With KOH; CH3OH cleavage;

1-formyl-1,12-dicarba-closo-dodecaborane (31726-43-9) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With potassium hydroxide cleavage;
With alcoholate In not given cleavage at room temp. with alcoholates;;
With KOH cleavage;

1,12-C2B10H11-1-Si(CH3)3 (60839-36-3) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With methanol; potassium hydroxide cleavage;
With KOH; CH3OH cleavage;

{(π-C2B10H12)2Co(III)}(1-) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
oxidn.;
oxidn.;

1,7-C2B10H11-1-COC6H5 (29985-59-9) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With methanol; potassium hydroxide Kinetics; 20°C, cleavage;
With KOH; CH3OH Kinetics; 20°C, cleavage;

1,2-C2B10H11-2-COC6H5 (15527-68-1) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With methanol; potassium hydroxide Kinetics; 20°C, cleavage;
With KOH; CH3OH Kinetics; 20°C, cleavage;

1-benzoyl-1,12-dicarba-closo-dodecaborane (24172-97-2) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With methanol; potassium hydroxide Kinetics; 20°C, cleavage;
With potassium hydroxide In ethanol; water Kinetics; decompn. by KOH in 80% C2H5OH at 20-50 °C;
With KOH; CH3OH Kinetics; 20°C, cleavage;

methanol (67-56-1) + 1-(trimethylstannyl)-1,12-dicarba-closo-dodecaborane (51375-18-9) + potassium hydroxide → 1,12-dicarbora-closo-dodecaborane (20644-12-6) + trimethyltin(IV) hydroxide (56-24-6)

Conditions	Yield
In methanol Kinetics; hydrolysis;;
In methanol

1.12-(CHO)2-1.12-C2B10H10 (38000-28-1) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With alcoholate In not given cleavage at room temp. with alcoholates;;

1-I-p-CB10H10CH (24491-89-2) → 1,7-dicarba-closo-dodecaborane(12) (16986-24-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With ammonia; sodium In ammonia byproducts: NH2(1-); redn. with 2 mol Na in NH3, processing with NH3;;

1-I-p-CB10H10CH (24491-89-2) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With water; sodium In ammonia byproducts: boric acid, I(1-); redn. with 2 mol Na in NH3, processing with H2O;;

2-iodo-closo-1,12-dodecaborane (22784-33-4) → 1,7-dicarba-closo-dodecaborane(12) (16986-24-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) + 9-iodo-m-carborane (17157-02-7) + 4-I-p-CB10H10CH (100187-58-4) + 2-Iodo-1,7-dicarba-closo-dodecaborane

Conditions	Yield
With potassium permanganate; sodium In ammonia redn. with 2 equival. Na in liq. NH3, oxidn. with KMnO4;; 5% p-carborane, 88% m-carborane, 7% 2-, 4-, 5-, 9-I-m-carborane (further product: 5-I-m-carborane);;

2-iodo-closo-1,12-dodecaborane (22784-33-4) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
With sodium In ammonia 2 equivalents Na;;

2-Chlor-p-carboran (22762-44-3) → 1,7-dicarba-closo-dodecaborane(12) (16986-24-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) + 9-chloro-m-carborane (17819-85-1) + 4-chloro-m-caborane (17819-86-2) + 2-chloro-m-caborane (22762-46-5)

Conditions	Yield
With potassium permanganate; sodium In ammonia redn. with 2 equival. Na in liq. NH3, oxidn. with KMnO4;; 7% p-carborane, 42% m-carborane, 22% 2-Cl-m-carborane, 2% 4-Cl-m-carborane, 6% 5-Cl-m-carborane (further product), 15% 9-Cl-m-carborane;;

1.12-(COC6H5)2-1.12-C2B10H10 (27120-67-8) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
In not given cleavage on basic aluminium oxide;;
With sodium ethanolate In ethanol
With sodium amide In ethanol
With NaNH2 In ethanol
With C2H5ONa In ethanol

1‐(mercapto)‐1,12‐dicarba‐closo‐dodecaborane(12) (69985-41-7) → 1,12-dicarbora-closo-dodecaborane (20644-12-6)

Conditions	Yield
at 400℃; Temperature;

1,12-dicarbora-closo-dodecaborane (20644-12-6) + benzoyl chloride (98-88-4) → 1-benzoyl-1,12-dicarba-closo-dodecaborane (24172-97-2)

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In diethyl ether; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: benzoyl chloride at 20℃; for 2h;	100%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + carbon dioxide (124-38-9) → 1,12-dihydroxycarbonyl-1,12-dicarba-closo-dodecaborane (23087-99-2)

Conditions	Yield
With hydrogenchloride	99%
With MeLi In diethyl ether

1,12-dicarbora-closo-dodecaborane (20644-12-6) + sodium hydroxide (1310-73-2) → 1,12-dihydroxy-1,12-dicarba-closo-dodecaborane (55629-27-1) + 1-hydroxy-1,12-dicarba-closo-dodecaborane(12) (54360-43-9)

Conditions	Yield
With n-BuLi; trimethyl borate; H2O2 In diethyl ether; hexane; water under Ar; n-BuLi (2.1 equiv.) in n-hexane added to carborane in ether (0°C); room temp., 1 h; B(OMe)3 (2.5 equiv.) added (-30°C); warmed (0°C, 1 h); H2O2 and HOAc added; room temp., 20 h; aq. NaHSO3 and NaOH added; room temp., 1 h; extd. with AcOEt; org. layer washed with H2O and brine; dried (MgSO4); concd.; residue purified by column chromy. (silica gel, AcOEt-n-hexane 1:5); elem. anal.;	A 96% B 4%
With n-BuLi; trimethyl borate; H2O2 In diethyl ether; hexane; water under Ar; n-BuLi (1.05 equiv.) in n-hexane added to carborane in ether (0°C); room temp., 1 h; B(OMe)3 (1.2 equiv.) added (-30°C);warmed (0°C, 1 h); H2O2 and HOAc added; room temp., 20 h; aq. Na HSO3 and NaOH added; room temp., 1 h; extd. with ether; org. layer washed with H2O and brine; dried (MgSO4); concd.; residue purified by column chromy. (silica gel, AcOEt-n-hexane 1:8);	A 1% B 85%

18-crown-6 ether (17455-13-9) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) → [potassium(18-crown-6 ether)][nido-2,9-C2B9H12] (82918-08-9)

Conditions	Yield
With potassium hydroxide In benzene Schlenk flask charged with 1,12-C2B10H12, 18-crown-6 (4 equiv), KOH anddistd. benzene, flask flushed with Ar, placed in 100°C oil bath,mixt. stirred under Ar for 42 h; cooled, ethanol added, soln. stirred for 15 min, filtered, solid washedwith 95% ethanol, distd. water, 95% ethanol, dissolved in acetone, filtered, mixed with water, concd., filtered, washed with water and small amt. of ethanol, dried, elem. anal.;	95%
With potassium hydroxide In ethanol; benzene Schlenk flask charged with 1,12-C2B10H12, 18-crown-6 (4 equiv), KOH anddistd. benzene/ethanol mixt. (9:1), flask flushed with Ar, placed in 100°C oil bath, mixt. stirred under Ar for 42 h; cooled, ethanol added, soln. stirred for 15 min, filtered, solid washedwith 95% ethanol, distd. water, 95% ethanol, dissolved in acetone, filtered, mixed with water, concd., filtered, washed with water and small amt. of ethanol, dried, elem. anal.;	20%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + Cyclopropanecarboxaldehyde (1489-69-6) → 1-cyclopropylhydroxymethyl-1,12-dicarba-closo-dodecaborane

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In 1,2-dimethoxyethane; hexane at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: Cyclopropanecarboxaldehyde In 1,2-dimethoxyethane; hexane at -78℃; for 4h; Inert atmosphere;	95%

1,12-dicarbora-closo-dodecaborane (20644-12-6) → 1,1'-bis(1,12-dicarba-closo-dodecaborane) (12547-78-3)

Conditions	Yield
With n-butyllithium; copper dichloride	94%

trimethylene oxide (503-30-0) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) → 1,12-bis(propan-1-ol)-1,12-closo-carborane (159227-72-2)

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In tetrahydrofuran; hexane at -78 - -20℃; for 3.5h; Inert atmosphere; Stage #2: trimethylene oxide In tetrahydrofuran; hexane at -78 - 20℃; for 15.5h; Inert atmosphere;	94%
With n-butyllithium In tetrahydrofuran 1.) 2 equiv. n-BuLi, 2.) trimethylene oxide; react. was quenched with 1 M HCl, crystn. from CHCl3;	92%

tetrahydrofuran (109-99-9) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) + mercury dichloride → bis[1,12-dicarba-closo-dodecaboran(12)-1-yl]mercury(II) tetrahydrofurane solvate

Conditions

Yield

With n-BuLi In diethyl ether; hexane to soln. p-C2B10H12 in dry Et2O at 273 K soln. of n-BuLi (1:1 mol) in hexane dropwise added; 45 min at 273 K; HgCl2 (0.5 mol) added; warmed to room temp. over period 45 min; reflux overnight; H2O added; organic layer washed (brine); combined aq. layers extd. (Et2O); combined organic layers dried (MgSO4), filtered, evapd. (vac.); flashchromy. (petroleum ether); crystd. (CH2Cl2:THF 1:1);

92%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + di-tert-butyl-diazodicarboxylate (870-50-8) → 1-((N,N'((tert-butyloxy)carbonyl)hydrazino))-1,12-dicarba-closo-dodecaborane (436863-27-3)

Conditions

Yield

With n-BuLi; HCl In diethyl ether n-BuLi in Et2O was added dropwise to p-carborane in Et2O over 5 min withstirring under Ar atm., react. mixt. was maintained at 0°C for 4 5 min and added to soln. DBAD in Et2O under Ar, react. mixt. was stirredfor 2.5 h at room temp.; solvent was evapd., water and HCl were added (pH 5), soln. was extd. with EtOAc, dried over MgSO4, solvent was evapd., chromy. on silica (petroleum ether-Et2O)and recrystn. from petroleum ether; elem. anal.;

91%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + perfluorotoluene (434-64-0) → 1,12-(4'-CF3C6F4)2-1,12-closo-C2B10H10 (1304037-88-4)

Conditions

Yield

With n-BuLi In tetrahydrofuran under N2; B compd. dissolved in dry degassed THF; treated with n-BuLi at0°C; stirred for 2 h; warmed to room temp.; cooled to 0°C ; C6F5CF3 added; stirred at room temp. for 18 h; satd. aq. NH4Cl added; aq. layer washed with Et2O; combined org. fractions concd. under reduced pressure; filtered through pad of silica with petroleum ether; soln. concd. under reduced pressure; oil crystd. slowly at room temp.; elem. anal.;

91%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + iodine (7553-56-2) → 2-iodo-closo-1,12-dodecaborane (22784-33-4)

Conditions	Yield
With H2SO4; HNO3 In acetic acid round-bottomed flask charged with dodecaborane-compd., I2 and glacial acetic acid, warmed to 60°C, concd. H2SO4 and concd. HNO3 (50:50, v/v) added dropwise in 40 min, stirred at 80°C for 1 h, cooled to room temp.; ice-cold H2O added, filtered, washed with H2O, dissolved in Et2O, diluteaq. Na2SO3 added, dried with MgSO4, filtered, solv. removed in vac., el em. anal.;	90%
With mercury(II) oxide In trifluoroacetic acid byproducts: HgI2; B-compd. addn. to soln. of HgO in CF3COOH, stirring (several hours, 20°C), excess Br2 addn.; soln. pouring to water, ppt. filtration off, drying, passing through column (SiO2, hexane), HgI2 elimination from soln., crystn.;	80%
aluminium trichloride In dichloromethane Ar-atmosphere; refluxing (3 d);	80%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + methyl trifluoromethanesulfonate (333-27-7) → deca-B-methyl-1,12-dicarba-closo-dodecaborane(12) (168098-42-8)

Conditions	Yield
With triflic acid In neat (no solvent) N2-atmosphere; refluxing (10 h); NaCl satd. soln. (H2O) addn., extg. (Et2O), drying (MgSO4), evapn. (vac.), pentane addn., filtering, evapn. (reduced pressure);	89%
In not given Ar atmosphere;

1,12-dicarbora-closo-dodecaborane (20644-12-6) + (2-bromoethynyl)trimethylsilane (18243-59-9) → 1-trimethylsilylethynyl-para-carborane (106898-21-9)

Conditions	Yield
With n-butyllithium; copper(l) chloride In tetrahydrofuran; diethyl ether N2; n-C4H9Li (hexane) added to p-carborane (abs. ether, 0-5°C, stirring); refluxed (5 min); cooled (-10 to -20°C); CuCl (THF) added; stirred (2 h); heated (40°C, 10 min); treated with alkyne (20°C, stirred, 1 h); refluxed 2 h; cooled to 0°C; treated with 5 % aq. HCl (stirring); extd. (ether); washed (5 % HCl, H2O to pH 7); dried (Na2SO4 or MgSO4); evapd.; column chromy. or distn. (vac.); elem. anal.;	86%
With C4H9Li; CuCl In pyridine; 1,2-dimethoxyethane; hexane addn. of BuLi in hexane to soln. of carborane in DME, addn. of CuCl and pyridine, heating at reflux for 30 min, addn. of BrCCSiMe3 on cooling, heating at reflux; addn. of ether, filtration, washing of filtrate with HCl(2.5M) and water, addn. of cyclohexane, passing through silica, removal of solvent, distillation in vac.;	76%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 4-methoxybenzenediazonium tetrafluoroborate (459-64-3) → C9H18B10N2O

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In diethyl ether at 0 - 20℃; for 2h; Inert atmosphere; Schlenk technique; Stage #2: 4-methoxybenzenediazonium tetrafluoroborate In diethyl ether at 0 - 20℃; for 12h; Inert atmosphere; Schlenk technique;	85%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 4-methoxybenzenediazonium tetrafluoroborate (459-64-3) → C16H24B10N4O2

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane In diethyl ether at 0 - 20℃; for 2h; Inert atmosphere; Schlenk technique; Stage #2: 4-methoxybenzenediazonium tetrafluoroborate In diethyl ether at 0 - 20℃; for 12h; Inert atmosphere; Schlenk technique;	85%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + carbon dioxide (124-38-9) + di-tert-butyl-diazodicarboxylate (870-50-8) → 1-((N,N'((tert-butyloxy)carbonyl)hydrazino))-1,12-dicarba-closo-dodecaborane-12-carboxylic acid (436863-28-4)

Conditions

Yield

With MeLi; n-BuLi; HCl In tetrahydrofuran; diethyl ether; hexane MeLi in Et2O was added to soln. p-carborane in Et2O at 0°C under Ar, stired for 45 min, DBAD in Et2O was added, allowed to warm to r.t., stirred for 2.5 h, cooled to 0°C, n-BuLi in hexane was added, stirred for 45 min, THF was added, CO2; was passed at -72°C for 3 h, react. mixt. was allowed to warm to r.t., solvent was evapd., water and HCl were added (pH 3), react. mixt. was extd. with EtOAc, dried over MgSO4 and evapd., residue was washed with petroleum ether and chromed.;

84%

chloropropionic acid (107-94-8) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) → C8H20B10O4

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In benzene for 2h; Inert atmosphere; Cooling with ice; Stage #2: chloropropionic acid In benzene for 4h;	83%

1,12-dicarbora-closo-dodecaborane (20644-12-6) → 2-iodo-closo-1,12-dodecaborane (22784-33-4)

Conditions	Yield
With iodine; silver trifluoroacetate In 1,2-dichloro-ethane byproducts: AgI; refluxed for 36 h, further CF3CO2Ag and I2 added at 6-h intervals untilthe condensate retained a weak color; cooled to 20°C; shaked with water; AgI filtered; org. layer washed (NaHSO3 soln.); evapd.; soln. of residue in pentane passed through an Al2O3 bed; pentane removed in vac.; recrystd. (pentane, 30 to -50°C);	81%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 4''-iodo[1,1';4',1'']terphenyl (1762-85-2) → 1-(4-terphenylyl)-p-carborane (1422458-69-2)

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium Stage #2: With copper(l) chloride Stage #3: 4''-iodo[1,1';4',1'']terphenyl	81%

1,12-dicarbora-closo-dodecaborane (20644-12-6) → 1,1'-bis(1,12-dicarba-closo-dodecaborane) (12547-78-3) + (C2B10H10)4H2

Conditions	Yield
With n-BuLi; CuCl2; H3O(1+) In diethyl ether refluxing (3 days);	A 80% B 16%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 1,4-bromoiodobenzene (589-87-7) → BrC6H4CB10H10CC6H4Br (894106-05-9)

Conditions	Yield
With n-butyllithium; copper(l) chloride In not given sublimation;	80%
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In tetrahydrofuran for 1h; Inert atmosphere; Cooling with ice; Stage #2: With copper(l) chloride In tetrahydrofuran at 25℃; for 1h; Stage #3: 1,4-bromoiodobenzene In tetrahydrofuran at 100℃; for 72h; Concentration; Temperature;

2-bromo-pyridine (109-04-6) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) → 1,7-di(2-pyridinyl)-di-1,7-dicarba-closo-dodecaborane (174002-64-3)

Conditions	Yield
With pyridine; n-butyllithium; copper(l) chloride In 1,2-dimethoxyethane N2-atmosphere; addn. of 1 equiv. BuLi (in hexanes) to carborane (in DME), addn. of pyridine and CuCl, refluxing for 30 min, distn. off of volatiles, addn. of 2 equiv. BrPy, refluxing for 48 h; chromy. (SiO2, CH2Cl2/cyclohexane=1:1);	79%
With pyridine; copper(l) iodide; n-butyllithium In 1,2-dimethoxyethane N2-atmosphere; addn. of 1 equiv. BuLi (in hexanes) to carborane (in DME), addn. of pyridine and CuI, refluxing for 30 min, distn. off of volatiles, addn. of 2 equiv. BrPy, refluxing for 60 h; addn. of ether with few drops H2O, standing overnight, filtration, washing (ether), addn. of 1 M HCl to filtrate, shaking with H2O, sepn. of org. layer, drying, evapn., recrystn. (EtOH, 5°C); second crop on evapn. of mother liquor; elem. anal.;	69%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + methyl thioisocyanate (556-61-6) → C6H18B10N2S2

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 1h; Stage #2: methyl thioisocyanate In diethyl ether; hexane at 20℃; for 24h;	79%

cyclohexanedione monoethylene ketal (4746-97-8) + 1,12-dicarbora-closo-dodecaborane (20644-12-6) → 8-(1,12-dicarba-closo-dodecaboran-1-yl)-1,4-dioxaspiro[4.5]decan-8-ol

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In diethyl ether; hexane at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: cyclohexanedione monoethylene ketal In diethyl ether; hexane at 0 - 20℃; for 1.5h;	78%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + phenyl isothiocyanate (103-72-0) → C16H22B10N2S2

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In diethyl ether; hexane at -78 - 20℃; for 1h; Stage #2: phenyl isothiocyanate In diethyl ether; hexane at 20℃; for 24h;	78%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + tetrabutylammonium tetramethyleneoxonium-undecahydro-closo-dodecaborate(1-) + cesium fluoride (13400-13-0) → Cs2[B12H11O(CH2)4-1,12-CB10H10CH]

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane n-BuLi soln. in hexane added at -78°C to a soln. of p-carborane in THF, stirred, heated to -30°C, (Bu4N)B12H11O(CH2)4 added, warmed slowly up to 10°C; chromd. (silica), dissolved in MeOH, treated with CsF in MeOH, ppt. filtered, washed (MeOH), dried (P2O5); elem. anal.;	77%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 3-chloropropan-1-amine (14753-26-5) → 1,12-bis(aminopropyl)-1,12-carborane (206347-25-3)

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In benzene for 2h; Inert atmosphere; Cooling with ice; Stage #2: 3-chloropropan-1-amine In benzene for 4h;	77%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + bromobutyric acid (2623-87-2) → C10H24B10O4

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In benzene for 2h; Inert atmosphere; Cooling with ice; Stage #2: bromobutyric acid In benzene for 4h;	77%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 3-ethyl-4-tert-butyldimethylsiloxyiodobenzene → 1-(4-tert-butyldimethylsiloxy-3-ethylphenyl)-1,12-dicarba-closo-dodecaborane

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In 1,2-dimethoxyethane; hexane at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: With copper(l) chloride In 1,2-dimethoxyethane; hexane at 20℃; for 1h; Inert atmosphere; Stage #3: 3-ethyl-4-tert-butyldimethylsiloxyiodobenzene With pyridine In 1,2-dimethoxyethane; hexane at 100℃; for 36h; Inert atmosphere;	77%

1,12-dicarbora-closo-dodecaborane (20644-12-6) + 3-iodobenzonitrile (69113-59-3) → 1-(3-cyanophenyl)-1,12-dicarba-closo-dodecaborane

Conditions	Yield
Stage #1: 1,12-dicarbora-closo-dodecaborane With n-butyllithium In 1,2-dimethoxyethane; hexane at 0 - 20℃; for 0.5h; Ullmann Condensation; Inert atmosphere; Stage #2: With copper(l) chloride In 1,2-dimethoxyethane; hexane at 20℃; for 1h; Ullmann Condensation; Inert atmosphere; Stage #3: 3-iodobenzonitrile With pyridine In 1,2-dimethoxyethane; hexane at 80℃; Ullmann Condensation; Inert atmosphere;	75%

Upstream product

• 17702-41-9 nido-decaborane 
• 74-86-2 acetylene 
• 16986-24-6 1,7-dicarba-closo-dodecaborane⁽¹²⁾ 
• 16872-09-6 1,2-dicarba-closo-dodecaborane⁽¹²⁾ 
• 51375-18-9 1-(trimethylstannyl)-1,12-dicarba-closo-dodecaborane 
• 31726-43-9 1-formyl-1,12-dicarba-closo-dodecaborane 
• 60839-36-3 1,12-C₂B₁₀H₁₁-1-Si(CH₃)3 
• 29985-59-9 1,7-C₂B₁₀H₁₁-1-COC₆H₅ 
• 15527-68-1 1,2-C₂B₁₀H₁₁-2-COC₆H₅ 
• 24172-97-2 1-benzoyl-1,12-dicarba-closo-dodecaborane 
• 67-56-1 methanol 
• 38000-28-1 1.12-(CHO)2-1.12-C₂B₁₀H₁₀ 
• 24491-89-2 1-I-p-CB₁₀H₁₀CH 
• 22784-33-4 2-iodo-closo-1,12-dodecaborane 

Downstream Products

• 16872-09-6 1,2-dicarba-closo-dodecaborane⁽¹²⁾ 
• 16986-24-6 1,7-dicarba-closo-dodecaborane⁽¹²⁾ 
• 53065-73-9 1-phenyl-1,12-dicarba-closo-dodecaborane 
• 78580-13-9 1,12-bis(p-methylbenzyl)-p-carbaborane 
• 189301-10-8 m-bis(1,12-dicarba-closo-dodecaboran-1-yl)benzene 
• 189301-08-4 1,3,5-tris(1,12-dicarba-closo-dodecaboran-1-yl)benzene 
• 191931-67-6 phenyl[4-(1,12-dicarba-closo-dodecaboran-1-yl)phenyl]acetylene 
• 191931-64-3 bis[4-(1,12-dicarba-closo-dodecaboran-1-yl)phenyl]acetylene 
• 396695-70-8 closo-1-diphenylmethylsilyl-1,12-dicarbadodecaborane⁽¹²⁾ 
• 396695-79-7 closo-1,12-bis(diphenylmethylsilyl)-1,12-dicarbadodecaborane⁽¹²⁾ 
• 620927-31-3 H(C₂B₁₀H₁₀C₆H₄)2I 
• 620927-32-4 C₂B₁₀H₁₀(C₆H₄C₂B₁₀H₁₁)2 
• 894106-05-9 BrC₆H₄CB₁₀H₁₀CC₆H₄Br 
• 934544-08-8 4,4-(PMe₂Ph)2-4,1,10-closo-PtC₂B₁₀H₁₂ 

Relevant articles and documents

METHOD FOR PREPARING PARA-CARBORANE USING MICROPOROUS MATERIALS

The present invention relates to a method of preparing para-carborane using a microporous material, the method is characterized by including: a mixing step for mixing ortho-carborane and a microporous material to prepare a mixture; a heat treatment step for isomerization which converts the ortho-carborane into para-carborane by heat treating the mixture, and thus obtaining a solution or a solid matter which contains the para-carborane; an extraction step for dissolving the solution or the solid matter in an organic solvent to extract an extract containing the para-carborane and the microporous material; and a separation step for separating the para-carborane from the extract.

Palladium-catalyzed amination of 2-Iodo-para-carborane

The palladium-catalyzed Buchwald-Hartwig amination of B-iodocarborane by various azoles and amines is described for the first time. The reactions of 2-iodo-p-carborane with indole, imidazole, benzimidazole, or carbazole in the system Pd(dba)2-BINAP-ButONa in dioxane at 100 °C gave 2-p-carboranyl derivatives of these azoles in high yields together with 2-hydroxy-p-carborane as a side product. The reactions of 2-iodo-p-carborane with aromatic amines in the same system gave the amination products in 60-70% yields and also were accompanied by the formation of hydroxy derivatives (up to 30% yields). In a special investigation it was shown that the base Bu tONa was responsible for its formation. The principle possibility of the amination of 2-iodo-p-carborane by morpholine (with 30% yield) as an example of aliphatic amination was shown. The structures of N-(1,12-dicarba-closo- dodecaboran-2-yl)carbazole (1), N-(1, 12-dicarba-closo-dodecaboran-2-yl) benzimidazole (2), N-(1, 12-dicarba-closo-dodecaboran-2-yl)indole (4), and 2-hydroxy-1,12-dicarba-closo-dodecaborane (5) have been established by X-ray diffraction studies.