Abstract:
PROBLEM TO BE SOLVED: To improve many features of the transition metal-catalyzed reactions, including the range of suitable substrates, the number of catalyst turnovers, reaction conditions, and efficiency.SOLUTION: This invention relates to: novel ligands for transition metals; and a process for using catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom bond- and carbon-carbon bond-forming reactions.
Abstract:
A compound selected from the group consisting of formula I-1, II-1, III-1 and IV-1: or a compound selected from the group consisting of: 2-(hydroxylamino)hexane, 3-(hydroxylamino)hexane, 2-(hydroxylamino)octane, and 3-(hydroxylamino)octane, wherein: R 7 and R 9 are independently linear C 2 -C 17 alkyl; R 11 is an unsubstituted linear C 2 -C 17 alkyl; R 8 is H or linear C 1 -C 8 alkyl; R 10 and R 14 are independently H, linear C 1 -C 8 alkyl, or CH 2 OH, or R 9 , R 10 , and the carbon to which they are attached form an eight membered cycloalkyl ring; R 12 is H, an unsubstituted linear C 1 -C 8 alkyl, or CH 2 OH, or R 11 , R 12 , and the carbon to which they are attached form a C 9 -C 11 cycloalkyl ring; R 13 is C 2 -C 20 alkyl, C 3 -C 12 cycloalkyl, aryl, or aryl-alkyl-; R 14 is H or C 1 -C 12 alkyl, or R 13 and R 14 together with the carbon to which they are attached form a C 3 -C 12 cycloalkyl ring; R 15 is H, or R 14 , R 15 , and the atoms to which they are attached form an oxazolidine ring that is optionally substituted with C 1 -C 6 alkyl; and R 16 is H, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, or aryl; provided that: when the compound is selected from formula I-1, the total number of carbons in R 7 and R 8 , together with the carbon to which they are attached, is 10 to 18; and the compound is not 1-nitrodecane, 2-nitrodecane, 1-nitroundecane, 2-nitroundecane, 3-nitroundecane, 4-nitroundecane, 5-nitroundecane, 6-nitroundecane, 1-nitrododecane, 2-nitrododecane, 3-nitrododecane, 4-nitrododecane, 5-nitrododecane, 6-nitrododecane, 1-nitrotridecane, 2-nitrotridecane, 3-nitrotridecane, 6-nitrotridecane, 1-nitrotetradecane, 1-nitropentadecane, 1-nitrohexadecane, 2-nitrohexadecane, 1-nitroheptadecane, 1-nitrooctadecane, or 2-nitrooctadecane; when the compound is selected from formula II-1, if R 10 is H or linear C 1 -C 8 alkyl, the total number of carbons in R 9 and R 10 , together with the carbon to which they are attached, is 5 to 18; or if R 10 is CH 2 OH, R 9 is linear C 12 -C 16 alkyl; and the compound is not 2-nitro-1-hexanol, 2-nitro-1-heptanol, 2-nitro-1-octanol, 2-methyl-2-nitro-1-heptanol, or 2-nitro-1-dodecanol; when the compound is selected from formula III-1, if R 12 is H or linear C 1 -C 8 alkyl, the total number of carbons in R 11 and R 12 , together with the carbon to which they are attached, is 6 to 18; or if R 12 is CH 2 OH, R 11 is linear C 7 -C 17 alkyl; and the compound is not 2-amino-1-heptanol, 2-amino-2-methyl-1-hexanol, 2-amino-1-octanol, 2-amino-2-ethyl-1-hexanol, 2-amino-1-nonanol, 2-amino-2-methyl-1-octanol, 2-amino-1-decanol, 2-amino-2-octyl-1,3-propanediol, 2-amino-2-butyl-1-hexanol, 2-amino-1-undecanol, 2-amino-1-dodecanol, 2-amino-2-decyl-1,3-propanediol, 2-amino-1-tridecanol, 2-amino-2-methyl-1-dodecanol, 2-amino-1-tetradecanol, 2-amino-2-dodecyl-1,3-propanediol, 2-amino-2-methyl-1-tridecanol, 2-amino-1-pentadecanol, 2-amino-2-tridecyl-1,3-propanediol, 2-amino-1-hexadecanol, 2-amino-2-tetradecyl-1,3-propanediol, 2-amino-2-methyl-1-pentadecanol, 2-amino-2-hexyl-1-decanol, 2-amino-1-heptadecanol, 2-amino-2-pentadecyl-1,3-propanediol, 2-amino-1-octadecanol, or 2-amino-2-hexadecyl-1,3-propanediol; and when the compound is selected from formula IV-1, if R 13 is an ethyl group, R 14 is not H; and the compound is not 5-propyl-1-aza-3,7-dioxabicyclo[3.3.0]octane, 4,4-diethyl-1-oxa-3-azacyclopentane, 3-oxa-1-azaspiro[4.4]nonane, 3-oxa-1-azaspiro[4.5]decane, or 3-oxa-1-azaspiro[4.7]dodecane.
Abstract:
One aspect of the present invention relates to novel ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject processes provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.
Abstract:
Provided is a process for the formation of nitrated compounds by the nitration of hydrocarbon compounds with dilute nitric acid. Also provided are processes for preparing industrially useful downstream derivatives of the nitrated compounds, as well as novel nitrated compounds and derivatives, and methods of using the derivatives in various applications.
Abstract:
In the invented process for producing a nitro compound, an organic substrate and nitrogen dioxide are reacted in the presence of oxygen or are reacted in a molar ratio of nitrogen dioxide to the organic substrate of less than 1 to yield a corresponding nitro compound. The reaction may be performed in the presence of N-hydroxyphthalimide or other imide compounds. Such organic substrates include (a) aliphatic hydrocarbons, (b) alicyclic hydrocarbons, (c) non-aromatic heterocyclic compounds each having a carbon atom on a ring, which carbon atom is bonded to a hydrogen atom, (d) compounds each having a carbon-hydrogen bond at the adjacent position to an aromatic ring, and (e) compounds each having a carbon-hydrogen bond at the adjacent position to a carbonyl group. This process can efficiently nitrate an organic substrate even under relatively mild conditions.