Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/02—Boron compounds
  • C07F5/022—Boron compounds without C-boron linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
  • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• This invention relates to the field of organic synthesis and to a process of forming a bis(azinyl)amine-BF 2 complex, where the boron atom is complexed by two ring nitrogens of a deprotonated bis(azinyl)amine compound, comprising reacting BF 3 with a protonated bis(azinyl) amine compound in the presence of polar aprotic organic solvent that is not reactive with the BF 3 under reaction conditions.
• Electroluminescent devices are well-known for their utility in providing light emissions.
• the emitting materials useful in such devices are bis(azinyl)amine-BF 2 complex, where the boron atom is complexed by two ring nitrogens of a deprotonated bis(azinyl)amine compound.
• Pending and commonly assigned U.S. Serial No. 10/183,242, filed June 27,2002 CIP of US Serial No 10/086,085 filed February 28,2002 teaches a method of preparing bis(azinyl)amine-BF 2 complexes by reacting BF 3 with a protonated bis(azinyl)amine compound in toluene as an organic solvent.
• the invention provides a process of forming a bis(azinyl)amine- BF 2 complex, where a boron atom is complexed by two ring nitrogens of a deprotonated bis(azinyl)amine compound, comprising the step of reacting BF 3 with a protonated bis(azinyl) amine in the presence of a polar aprotic organic solvent that is not reactive with the BF 3 under reaction conditions.
• Such process provides good yields, even when a bulky group is present on the bis(azinyl)amine compound.
• the process enables synthesis of bis(azinyl)amine-BF complexes by reacting a protonated bis(azinyl)amine compound with BF 3 or a BF 3 source in high yield.
• protonated means that at least one nitrogen atom of the compound is substituted with a hydrogen atom.
• the protonated bis(azinyl)amine reactant compound may be usefully represented by Formula (1):
• a and A' represent independent azine ring systems corresponding to 6- membered aromatic ring systems containing at least one nitrogen; each X a and X b is an independently selected substituent, two of which may join to form a fused ring to A or A', and m and n are independently 0 to 4; and atoms 1, 2, 3, 4, 1', 2', 3', and 4' are independently selected as either carbon or nitrogen atoms.
• the compound represented by Formula 1 is reacted with either BF3 or BF 3 source, for example Et 2 O- BF 3 .
• Other BF 3 sources include but are not limited to Me 2 O- BF 3 , THF- BF 3 , Me 2 S- BF 3 .
• the amount of BF 3 used in this process, relative to the starting material as per formula (1), can range from 1-50 equivalents.
• the resulting product of this process is depicted by Formula (2):
• Ri, R 2 and R 3 each independently represents hydrogen, fluorine, alkyl, aryl, alkoxy, aryloxy, dialkylamino, diarylamino, cyano, or nitro groups; and Ri and R 2 , R 2 and R 3 or R] and R 3 may join to form a cycloalyl or an aryl ring group.
• Typical substituents include alkyl, aryl alkoxy, aryloxy, dialkylamino, diarylamino, cyano, or nitro groups.
• the various alkyl groups, such as perfluoroalkyl groups typically contain 1 to 6 carbon atoms, but less than 12 carbon atoms.
• the cycloalkyl moieties usually contain from 3 to 10 carbon atoms, but typically contain five or six carbon atoms — e.g., cyclopentyl or cyclohexyl structure.
• the aryl groups are usually phenyl moieties.
• boron compounds complexed by two ring nitrogens of a deprotonated bis(azinyl)amine compound that can be prepared using the present invention are the following:
• the temperature needed to effect the formation of the complex depicted in formula (2) is typically room temperature (18°C) to 200°C. Conveniently the reaction is carried out at temperature of at least 80°C. The temperature requirements can be also dictated by the nature of the substituents described in Formulas (1) and (2) and the solubility of the starting ligand (1). Unless otherwise specifically stated, use of the term "substituted” or “substituent” means any group or atom other than hydrogen.
• a substituent group when a substituent group contains a substitutable hydrogen, it is also intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any substituent group or groups as herein mentioned.
• a substituent group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, sulfur, selenium, or boron.
• the substituent may be, for example, halogen, such as chloro, bromo or fluoro; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain or cyclic alkyl, such as methyl, trifluoromethyl, ethyl, t- butyl, cyclohexyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2- methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di- t-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl,
• the substituents may themselves be further substituted one or more times with the described substituent groups.
• the particular substituents used may be selected by those skilled in the art to attain the desired desirable properties for a specific application and can include, for example, electron-withdrawing groups, electron-donating groups, and steric groups.
• the substituents may be joined together to form a ring such as a fused ring unless otherwise provided.
• the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
• the water mixture was stirred (1-3 h) to solidified product which was isolated by filtration, washed with water (400 ml), saturated sodium bicarbonate (400 ml), water (3x400ml) and dried with flow of air for 3 hours.
• the crude product was transferred to flask, slurry with i-Pr 2 O (600 mL), stirred for 0.5h, filtered off, washed with Et 2 O (250 mL) and dried with flow of air for l-2h and then in vacuum oven at 70°C for 6-12 hours to yield 119.6 g (83%) of the desire product - Inv 7.
• Table 1 shows that, for the samples tested, the yields using innovative process range from 70-91% yield, while those for the comparative process ranged from 0-4%. Poor results with bulky substituents wee also observed with solvents such as DMSO and DMF.
• solvents such as DMSO and DMF.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Quinoline Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

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• 2003
  • 2003-12-11 US US10/733,086 patent/US6903214B1/en not_active Expired - Lifetime
• 2004
  • 2004-11-29 KR KR1020067011354A patent/KR101038247B1/ko not_active Expired - Lifetime
  • 2004-11-29 WO PCT/US2004/039869 patent/WO2005061521A1/en not_active Ceased
  • 2004-11-29 JP JP2006543860A patent/JP4891780B2/ja not_active Expired - Lifetime
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