A process produces an organic compound by allowing (A) a compound capable of generating a free radical to react with (B) at least one of esters and salts of nitrous acid in the presence of a nitrogen-containing cyclic compound constitutively having a skeleton represented by following Formula (i) in its ring:

1. Field of the Invention
The present invention relates to a process for producing organic compounds each having, for example, a nitrogen-containing group, an oxygen-containing group, or a carbon-carbon unsaturated bond-containing group using a nitrous ester and/or nitrite.
2. Description of the Related Art
Oximes and other organic compounds each having a nitrogen-containing group are useful as intermediate materials for monomers for the production of polymeric compounds or as intermediates in the synthesis of fine chemicals. For example, cycloalkanone oximes are very important as intermediate materials for polyamides. Such cycloalkanone oximes have been conventionally produced by, for example, a process of subjecting a cycloalkanone and hydroxylamine to dehydration condensation, a process of catalytically hydrogenating a nitrocycloalkenone in the presence of a palladium catalyst, or a process of subjecting a hydroxyaminocycloalkane to air oxidation in the presence of a divalent cobalt. However, these processes require relatively expensive material compounds.
Cyclohexanone oxime is commercially produced by a process in which cyclohexane is irradiated with radiation in the presence of nitrosyl chloride to thereby yield cyclohexanone oxime via nitrosocyclohexane. This process can directly convert cyclohexane into cyclohexanone oxime and can thereby reduce production costs. However, nitrosyl chloride used as a raw material is generally prepared by a reaction between nitrogen monoxide and chlorine, thus invites complicated facilities and decreased operability and imposes heavy loads on the environment.
As a possible solution to these problems, for example, Japanese Examined Patent Application Publication No. 02-13659 discloses a process of allowing a cycloalkane to come in contact with a nitrous ester in a gas phase at a temperature of 150xc2x0 C. to 400xc2x0 C. to thereby yield a cycloalkanone oxime. This process, however, requires severe reaction conditions and exhibits a low space-time yield.
Accordingly, an object of the present invention is to provide a process for easily producing a nitrogen-containing organic compound such as an oxime from low-cost materials under mild conditions.
Another object of the present invention is to provide a process for efficiently producing an organic compound having, for example, a nitrogen-containing group, an oxygen-containing group, or a carbon-carbon unsaturated bond-containing group using an ester or salt of nitrous acid.
Yet another object of the present invention is to provide a process for selectively producing a nitroso compound or a dimer thereof in a high yield.
Still another object of the present invention is to provide a process for selectively and efficiently producing an oxime.
After intensive investigations to achieve the objects, the present inventors have found organic compounds each having, for example, a nitrogen-containing group, an oxygen-containing group, or a carbon-carbon unsaturated bond-containing group can be produced in good yields by allowing a compound capable of generating a free radical to react with at least one of esters and salts of nitrous acid in the presence of a nitrogen-containing cyclic compound having a specific structure. The present invention has been accomplished based on these findings.
Specifically, the present invention provides a process for producing an organic compound, including allowing (A) a compound capable of generating a free radical to react with (B) at least one of esters and salts of nitrous acid in the presence of a nitrogen-containing cyclic compound constitutively having a skeleton represented by following Formula (i) in its ring:
wherein X is one of an oxygen atom and an xe2x80x94OR group, and wherein R is one of a hydrogen atom and a hydroxyl-protecting group.
By this procedure, oxime compounds and other nitrogen-containing organic compounds having a nitrogen-containing group combined with a radical generating site of the compound (A) capable of generating a free radical; oxygen-containing organic compounds having an oxygen-containing group combined with the radical generating site; and organic compounds having a carbon-carbon unsaturated bond-containing group and other products can be efficiently produced from easily available raw materials by easy and simple procedures under mild conditions.
Examples of the nitrogen-containing cyclic compound include cyclic imide compounds having a cyclic imide skeleton represented by following Formula (I):
wherein n is one of 0 and 1; X is one of an oxygen atom and an xe2x80x94OR group, and wherein R is one of a hydrogen atom and a hydroxyl-protecting group.
Examples of the nitrogen-containing cyclic compound also include compounds represented by following Formula (1):
wherein n is one of 0 and 1;
X is one of an oxygen atom and an xe2x80x94OR group,
wherein R is one of a hydrogen atom and a hydroxyl-protecting group;
R1, R2, R3, R4, R5, and R6 are the same or different and are each one of hydrogen atom, halogen atoms, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, and acyloxy groups,
wherein at least two of R1, R2, R3, R4, R5, and R6 may be combined to form a double bond, an aromatic ring, or a non-aromatic ring with a carbon atom or a carbon-carbon bond constituting the cyclic imide skeleton, and
wherein one or more of N-substituted cyclic imide group represented by following Formula (a):
wherein n and X have the same meanings as defined above, may be further formed on at least one of R1, R2, R3, R4, R5, and R6 or at least one of the double bond, the aromatic ring and the non-aromatic ring formed by at least two of R1, R2, R3, R4, R5, and R6.
Examples of the compound (A) capable of generating a free radical include (A1) aromatic compounds and unsaturated compounds each having a methyl group or methylene group at the adjacent position to an aromatic ring or an unsaturated bond; (A2) non-aromatic cyclic compounds each constitutively having a methylene group in their ring; and (A3) compounds each having a methine carbon atom.
In the process, an oxime compound may be formed as a result of a reaction.
In the process, the nitrous ester or nitrite (B) may be added to reaction system intermittently in plural installments or continuously. By this procedure, a nitroso compound or its dimer, or an oxime compound in a further proceeded reaction can be selectively produced in a high yield. The process may further include allowing the compound (A) capable of generating a free radical to react with the at least one of esters and salts of nitrous acid (B) to thereby yield a nitroso compound or a dimer thereof. The process may also further include the steps of allowing the compound (A) capable of generating a free radical to react with the at least one of esters and salts of nitrous acid (B) to thereby yield a nitroso compound or a dimer thereof; and converting the formed nitroso compound or a dimer thereof into an oxime compound. Thus, an oxime compound can be selectively and efficiently produced.
Further objects, features and advantages of the present invention will become apparent from the following description of the preferred embodiments.
Nitrogen-Containing Cyclic Compounds
At least one nitrogen-containing cyclic compound constitutively having a skeleton represented by Formula (i) in its ring is used as a catalyst in the present invention.
In Formula (i), the bond between a nitrogen atom and X is a single or double bond. The nitrogen-containing cyclic compound may intramolecularly have a plurality of the skeleton represented by Formula (i). When X is an xe2x80x94OR group and R is a hydroxyl-protecting group, the nitrogen-containing cyclic compound may have a plurality of moieties combined through R, which moieties are derived from the skeleton represented by Formula (i) by removal of R.
Examples of the hydroxyl-protecting group represented by R in Formula (i) are hydroxyl-protecting groups conventionally used in the field of organic synthesis. Such hydroxyl-protecting groups include, but are not limited to, alkyl groups (e.g., methyl, t-butyl, and other C1-C4 alkyl groups), alkenyl groups (e.g., allyl group), cycloalkyl groups (e.g., cyclohexyl group), aryl groups (e.g., 2,4-dinitrophenyl group), aralkyl groups (e.g., benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, and triphenylmethyl groups); substituted methyl groups (e.g., methoxymethyl, methylthiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, and 2-(trimethylsilyl)ethoxymethyl groups), substituted ethyl groups (e.g., 1-ethoxyethyl, 1-methyl-1-methoxyethyl, 1-isopropoxyethyl, 2,2,2-trichloroethyl, and 2-methoxyethyl groups), tetrahydropyranyl group, tetrahydrofuranyl group, 1-hydroxyalkyl groups (e.g., 1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxydecyl, 1-hydroxyhexadecyl, 1-hydroxy-1-phenylmethyl groups), and other groups capable of forming an acetal or hemiacetal group with a hydroxyl group; acyl groups (e.g., formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, and other aliphatic C1-C20 acyl groups, and other aliphatic unsaturated or saturated acyl groups; acetoacetyl group; cyclopentanecarbonyl, cyclohexanecarbonyl, other cycloalkanecarbonyl groups, and other alicyclic acyl groups; benzoyl, naphthoyl, and other aromatic acyl groups), sulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, and naphthalenesulfonyl groups), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and other C1-C4 alkoxy-carbonyl groups), aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl, and p-methoxybenzyloxycarbonyl groups), substituted or unsubstituted carbamoyl groups (e.g., carbamoyl, methylcarbamoyl, and phenylcarbamoyl groups), groups derived from inorganic acids (e.g., sulfuric acid, nitric acid, phosphoric acid, and boric acid) by removal of OH group, dialkylphosphinothioyl groups (e.g., dimethylphosphinothioyl group), diarylphosphinothioyl groups (e.g., diphenylphosphinothioyl group), and substituted silyl groups (e.g., trimethylsilyl, t-butyldimethylsilyl, tribenzylsilyl, and triphenylsilyl groups).
When X is an xe2x80x94OR group, a plurality of moieties may be combined through R, which moieties are derived from the skeleton of Formula (i) by removal of R. In this case, R includes, for example, oxalyl, malonyl, succinyl, glutaryl, adipoyl, phthaloyl, isophthaloyl, terephthaloyl, and other polycarboxylic acyl groups; carbonyl group; methylene, ethylidene, isopropylidene, cyclopentylidene, cyclohexylidene, benzylidene, and other polyvalent hydrocarbon groups, of which groups capable of forming an acetal bond with two hydroxyl groups are preferred.
Preferred examples of R are hydrogen atom; groups capable of forming an acetal or hemiacetal group (bond) with a hydroxyl group; acyl groups, sulfonyl groups, alkoxycarbonyl groups, carbamoyl groups, and other groups derived from acids (e.g., carboxylic acids, sulfonic acids, carbonic acid, carbamic acid, sulfuric acid, phosphoric acids, and boric acids) by removal of OH group, and other hydrolyzable protecting groups that can be eliminated by hydrolysis.
The nitrogen-containing cyclic compounds include, but are not limited to, cyclic imide compounds each having a N-substituted cyclic imide skeleton represented by Formula (I). These cyclic imide compounds may intramolecularly have a plurality of the N-substituted imide skeleton represented by Formula (I). When X is an xe2x80x94OR group and R is a hydroxyl-protecting group, the cyclic imide compounds may have a plurality of moieties (N-oxy cyclic imide skeletons) combined through R, which moieties are derived from the N-substituted cyclic imide skeleton represented by Formula (I) by removal of R.
In Formula (I), n is 0 or 1. Specifically, Formula (I) represents a five-membered N-substituted cyclic imide skeleton when n is 0 and represents a six-membered N-substituted cyclic imide skeleton when n is 1.
Typical examples of the imide compounds are imide compounds represented by Formula (1). In the substituents R1, R2, R3, R4, R5, and R6 in the imide compounds of Formula (1), the halogen atoms include iodine, bromine, chlorine, and fluorine atoms. The alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, decyl, dodecyl, tetradecyl, hexadecyl, and other straight- or branched-chain alkyl groups each containing from about 1 to about 30 carbon atoms, of which those each containing from about 1 to about 20 carbon atoms are preferred.
The aryl groups include, for example, phenyl, tolyl, xylyl, and naphthyl groups. The cycloalkyl groups include, for example, cyclopentyl and cyclohexyl groups. The alkoxy groups include, for example, methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, octadecyloxy, and other alkoxy groups each containing from about 1 to about 30 carbon atoms, of which alkoxy groups each containing from about 1 to about 20 carbon atoms are preferred.
The substituted oxycarbonyl groups include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl, decyloxycarbonyl, hexadecyloxycarbonyl, and other C1-C30 alkoxy-carbonyl groups, of which C1-C20 alkoxy-carbonyl groups are preferred; cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, and other cycloalkyloxycarbonyl groups, of which cycloalkyloxycarbonyl groups each having 3 to 20 members are preferred; phenyloxycarbonyl, naphthyloxycarbonyl, and other aryloxycarbonyl groups, of which C6-C20 aryloxy-carbonyl groups are preferred; benzyloxycarbonyl, and other aralkyloxycarbonyl groups, of which C7-C21 aralkyloxy-carbonyl groups are preferred.
The acyl groups include, but are not limited to, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, decanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, other aliphatic C1-C30 acyl groups, and other unsaturated or saturated aliphatic acyl groups, of which aliphatic C1-C20 acyl groups are preferred; acetoacetyl group; cyclopentanecarbonyl, cyclohexanecarbonyl, other cycloalkanecarbonyl, and other alicyclic acyl groups; benzoyl, naphthoyl, and other aromatic acyl groups.
The acyloxy groups include, but are not limited to, formyloxy, acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, pivaloyloxy, hexanoyloxy, octanoyloxy, decanoyloxy, lauroyloxy, myristoyloxy, palmitoyloxy, stearoyloxy, other aliphatic C1-C30 acyloxy groups, and other unsaturated or saturated aliphatic acyloxy groups, of which C1-C20 acyloxy groups are preferred; acetoacetyloxy group; cyclopentanecarbonyloxy, cyclohexanecarbonyloxy, other cycloalkanecarbonyloxy, and other alicyclic acyloxy groups; benzoyloxy, naphthoyloxy, and other aromatic acyloxy groups.
The substituents R1, R2, R3, R4, R5, and R6 may be the same with or different from one another. At least two of R1, R2, R3, R4, R5, and R6 in Formula (1) may be combined to form a double bond, an aromatic ring, or a non-aromatic ring with a carbon atom or carbon-carbon bond constituting the cyclic imide skeleton. The aromatic or non-aromatic ring contains preferably from about 5 to about 12 members and more preferably from about 6 to about 10 members. The ring may be a heterocyclic ring or condensed heterocyclic ring, but it is often a hydrocarbon ring. Such rings include, for example, non-aromatic alicyclic rings (e.g., cyclohexane ring and other cycloalkane rings which may have at least one substituent, cyclohexene ring and other cycloalkene rings which may have at least one substituent), non-aromatic bridged rings (e.g., 5-norbornene ring and other bridged hydrocarbon rings which may have at least one substituent), benzene ring, naphthalene ring, and other aromatic rings (including condensed rings) which may have at least one substituent. The ring often comprises an aromatic ring. The ring may have at least one substituent. Such substituents include, but are not limited to, alkyl groups, haloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, acyloxy groups, nitro group, cyano group, amino group, and halogen atoms.
One or more of the N-substituted cyclic imide group represented by Formula (a) may be further formed on at least one of R1, R2, R3, R4, R5, and R6 and/or on the double bond, aromatic ring, or non-aromatic ring formed by the at least two of R1, R2, R3, R4, R5, and R6. For example, when at least one of R1, R2, R3, R4, R5, and R6 is an alkyl group containing two or more carbon atoms, the N-substituted cyclic imide group maybe formed with adjacent two carbon atoms constituting the alkyl group. Likewise, when at least two of R1, R2, R3, R4, R5, and R6 are combined to form a double bond with a carbon-carbon bond constituting the cyclic imide skeleton, the N-substituted cyclic imide group may be formed with the double bond. When at least two of R1, R2, R3, R4, R5, and R6 are combined to form an aromatic or non-aromatic ring with a carbon atom or carbon-carbon bond constituting the cyclic imide skeleton, the N-substituted cyclic imide group may be formed with adjacent two carbon atoms constituting the ring.
Preferred imide compounds include compounds represented by following formulae:
wherein R11, R12, R13, R14, R15, and R16 are the same or different and are each one of hydrogen atom, halogen atoms, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, and acyloxy groups;
R17, R18, R19, R20, R21, R22, R23, R24, R25, and R26 are the same or different and are each one of hydrogen atom, alkyl groups, haloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, acyloxy groups, nitro group, cyano group, amino group, and halogen atoms,
wherein adjacent two of R17 to R26 may be combined to form a five- or six-membered N-substituted cyclic imide skeleton indicated in one of Formulae (1c), (1d), (1e), (1f), (1h), and (1i);
A in Formula (1f) is a methylene group or an oxygen atom; and
X has the same meaning as defined above.
The halogen atoms, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, and acyloxy groups in the substituents R11 to R16 include the same groups as in the corresponding groups in the substituents R1 to R6.
In the substituents R17 to R26, the alkyl groups include the same alkyl groups as those exemplified above, of which alkyl groups each containing from about 1 to about 6 carbon atoms are preferred. The haloalkyl groups include, for example, trifluoromethyl group, and other haloalkyl groups each containing from about 1 to about 4 carbon atoms. The alkoxy groups include the same alkoxy groups as those exemplified above, of which lower alkoxy groups each containing from about 1 to about 4 carbon atoms are preferred. The substituted oxycarbonyl groups include the same substituted oxycarbonyl groups as those exemplified above, such as alkoxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, and aralkyloxycarbonyl groups. The acyl groups include aliphatic unsaturated or saturated acyl groups, acetoacetyl group, alicyclic acyl groups, aromatic acyl groups, and other acyl groups as exemplified above. The acyloxy groups include aliphatic unsaturated or saturated acyloxy groups, acetoacetyloxy group, alicyclic acyloxy groups, aromatic acyloxy groups, and other acyloxy groups as exemplified above. The halogen atoms include, for example, fluorine, chlorine, and bromine atoms. Each of the substituents R17 to R26 is often one of hydrogen atom, lower alkyl groups each containing from about 1 to about 4 carbon atoms, carboxyl group, substituted oxycarbonyl groups, nitro group, and halogen atoms.
Examples of preferred imide compounds having a five-membered N-substituted cyclic imide skeleton are N-hydroxysuccinimide, N-hydroxy-xcex1-methylsuccinimide, N-hydroxy-xcex1,xcex1-dimethylsuccinimide, N-hydroxy-xcex1,xcex2-dimethylsuccinimide, N-hydroxy-xcex1,xcex1,xcex2,xcex2-tetramethylsuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N,Nxe2x80x2-dihydroxycyclohexanetetracarboxylic diimide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxychlorendimide, N-hydroxyhimimide, N-hydroxytrimellitimide, N,Nxe2x80x2-dihydroxypyromellitic diimide, N,Nxe2x80x2-dihydroxynaphthalenetetracarboxylic diimide, xcex1,xcex2-diacetoxy-N-hydroxysuccinimide, N-hydroxy-xcex1,xcex2-bis(propionyloxy)succinimide, N-hydroxy-xcex1,xcex2-bis(valeryloxy)succinimide, N-hydroxy-xcex1,xcex2-bis(lauroyloxy)succinimide, xcex1,xcex2-bis(benzoyloxy)-N-hydroxysuccinimide, N-hydroxy-4-methoxycarbonylphthalimide, 4-chloro-N-hydroxyphthalimide, 4-ethoxycarbonyl-N-hydroxyphthalimide, N-hydroxy-4-pentyloxycarbonylphthalimide, 4-dodecyloxy-N-hydroxycarbonylphthalimide, N-hydroxy-4-phenoxycarbonylphthalimide, N-hydroxy-4,5-bis(methoxycarbonyl)phthalimide, 4,5-bis(ethoxycarbonyl)-N-hydroxyphthalimide, N-hydroxy-4,5-bis(pentyloxycarbonyl)phthalimide, 4,5-bis(dodecyloxycarbonyl)-N-hydroxyphthalimide, N-hydroxy-4,5-bis(phenoxycarbonyl)phthalimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a hydrogen atom; compounds corresponding to these compounds, except with R of an acyl group such as acetyl group, propionyl group, and benzoyl group; N-methoxymethyloxyphthalimide, N-(2-methoxyethoxymethyloxy)phthalimide, N-tetrahydropyranyloxyphthalimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a group capable of forming an acetal or hemiacetal bond with a hydroxyl group; N-methanesulfonyloxyphthalimide, N-(p-toluenesulfonyloxy)phthalimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a sulfonyl group; sulfuric esters, nitric esters, phosphoric esters, and boric esters of N-hydroxyphthalimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a group derived from an inorganic acid by removal of OH group.
Examples of preferred imide compounds each having a six-membered N-substituted cyclic imide skeleton are N-hydroxyglutarimide, N-hydroxy-xcex1,xcex1-dimethylglutarimide, N-hydroxy-xcex2,xcex2-dimethylglutarimide, N-hydroxy-1,8-decalindicarboximide, N,Nxe2x80x2-dihydroxy-1,8;4,5-decalintetracarboxylic diimide, N-hydroxy-1,8-naphthalenedicarboximide (N-hyrdoxynaphthalimide), N,Nxe2x80x2-dihydroxy-1,8;4,5-naphthalenetetracarboxylic diimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a hydrogen atom; compounds corresponding to these compounds except with R of an acyl group such as acetyl group, propionyl group, and benzoyl group; N-methoxymethyloxy-1,8-naphthalenedicarboximide, N,Nxe2x80x2-bis(methoxymethyloxy)-1,8;4,5-naphthalenetetracarboxylic diimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a group capable of forming an acetal or hemiacetal bond with a hydroxyl group; N-methanesulfonyloxy-1,8-naphthalenedicarboximide, N,Nxe2x80x2-bis(methanesulfonyloxy)-1,8;4,5-naphthalenetetracarboxylic diimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a sulfonyl group; sulfuric esters, nitric esters, phosphoric esters, and boric esters of N-hydroxy-1,8-naphthalenedicarboximide and N,Nxe2x80x2-dihydroxy-1,8;4,5-naphthalenetetracarboxylic diimide, and other compounds of Formula (1) wherein X is an xe2x80x94OR group and R is a group derived from an inorganic acid by removal of OH group.
In addition to the cyclic imide compounds, the nitrogen-containing cyclic compounds include, for example, cyclic acylurea compounds each having a cyclic acylurea skeleton [xe2x80x94C(xe2x95x90O)xe2x80x94Nxe2x80x94C(xe2x95x90O)xe2x80x94Nxe2x80x94] represented by following Formula (II):
wherein G is one of a carbon atom and a nitrogen atom; m is one of 1 and 2, and, when m is 2, two Gs may be the same or different; and R has the same meaning as defined above. These cyclic acylurea compounds may each intramolecularly have a plurality of the cyclic acylurea skeleton represented by Formula (II). They also may have a plurality of moieties (N-oxy cyclic acylurea skeletons) combined through R, which moieties are derived from the cyclic acylurea skeleton of Formula (II) by removal of R. The atom G and the nitrogen atom combined with G constituting the cyclic acylurea skeleton may have at least one substituent. The cyclic acylurea skeleton may further have a non-aromatic or aromatic ring condensed therewith and/or may have a double bond in its ring.
The cyclic acylurea skeletons represented by Formula (II) include a 3-hydroxy (or 3-substituted oxy) hydantoin skeleton represented by following Formula (IIa); a 4-hydroxy (or 4-substituted oxy)-1,2,4-triazolidine-3,5-dione skeleton [inclusive of a 4-hydroxy (or 4-substituted oxy)-1,2,4-triazoline-3,5-dione skeleton]] represented by following Formula (IIb); a hydro-3-hydroxy (or 3-substituted oxy)-1,3-diazine-2,4-dione skeleton [inclusive of a hexahydro-1-hydroxy (or 1-substituted oxy)-1,3-diazine-2,4,6-trione skeleton, a hexahydro-1,3-dihydroxy (or 1,3-bis-substituted oxy)-1,3-diazine-2,4,6-trione skeleton, and a 3-hydroxy (or 3-substituted oxy) uracil skeleton] represented by following Formula (IIc); a hydro-4-hydroxy (or 4-substituted oxy)-1,2,4-triazine-3,5-dione skeleton represented by following Formula (IId); a hydro-1-hydroxy (or 1-substituted oxy)-1,3,5-triazine-2,6-dione skeleton represented by following Formula (IIe); and a hydro-5-hydroxy (or 5-substituted oxy)-1,2,3,5-tetrazine-4,6-dione skeleton represented by following Formula (IIf):
wherein R has the same meaning as defined above.
Typical examples of the cyclic acylurea compounds are hydro-1-hydroxy (or 1-substituted oxy)-1,3,5-triazine-2,6-dione compounds represented by following Formula (2):
wherein Ra and Rd are the same or different and are each one of hydrogen atom, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl groups which may be protected by a protecting group, carboxyl groups which may be protected by a protecting group, and acyl groups;
Rb and Rc are the same or different and are each one of hydrogen atom, halogen atoms, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, and acyloxy groups,
wherein at least two of Ra, Rb, Rc, and Rd may be combined to form one of a double bond, an aromatic ring, or a non-aromatic ring with an atom constituting the ring in the formula,
wherein Rb and Rc may together form an oxo group; and
R has the same meaning as defined above.
In Formula (2), the alkyl groups, aryl groups, cycloalkyl groups, and acyl groups in Ra and Rb are similar to those exemplified in the substituents R1 to R6. The hydroxyl-protecting group herein includes similar hydroxyl-protecting groups as exemplified above.
Examples of the carboxyl-protecting group include protecting groups conventionally used in the field of organic synthesis. Such carboxyl-protecting groups include, but are not limited to, methoxy, ethoxy, butoxy, and other C1-C6 alkoxy groups, and other alkoxy groups; cycloalkyloxy groups; phenoxy group, and other aryloxy groups; benzyloxy, and other aralkyloxy groups; trimethylsilyloxy group, and other trialkylsilyloxy groups; amino group, methylamino group, dimethylamino group, and other mono- or di-C1-C6 alkyl-amino groups, and other amino groups which may have at least one substituent.
Examples of the halogen atoms, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups, carboxy group, substituted oxycarbonyl groups, acyl groups, and acyloxy groups in Rb and Rc are similar to those exemplified in the substituents R1 to R6.
At least two of Ra, Rb, Rc, and Rd may be combined to form one of a double bond, an aromatic ring, and a non-aromatic ring with at least one atom (a carbon atom and/or a nitrogen atom) constituting the ring in Formula (2), and Rb and Rc may together form an oxo group. Preferred examples of the aromatic ring and the non-aromatic ring are similar to those exemplified above.
Preferred examples of the cyclic acylurea compounds are 3-hydroxyhydantoin, 1,3-dihydroxyhydantoin, 3-hydroxy-1-methylhydantoin, 3-acetoxyhydantoin, 1,3-diacetoxyhydantoin, 3-acetoxy-1-methylhydantoin, 3-benzoyloxyhydantoin, 1,3-bis(benzoyloxy)hydantoin, 3-benzoyloxy-1-methylhydantoin, and other compounds each having the skeleton represented by Formula (IIa); 4-hydroxy-1,2,4-triazolidine-3,5-dione, 4-hydroxy-1,2-dimethyl-1,2,4-triazolidine-3,5-dione, 4-acetoxy-1,2,4-triazolidine-3,5-dione, 4-acetoxy-1,2-dimethyl-1,2,4-triazolidine-3,5-dione, 4-benzoyloxy-1,2,4-triazolidine-3,5-dione, 4-benzoyloxy-1,2-dimethyl-1,2,4-triazolidine-3,5-dione, 4-hydroxy-1,2,4-triazoline-3,5-dione, 4-acetoxy-1,2,4-triazoline-3,5-dione, 4-benzoyloxy-1,2,4-triazoline-3,5-dione, and other compounds having the skeleton represented by Formula (IIb); hexahydro-3-hydroxy-1,3-diazine-2,4-dione, hexahydro-1,3-dihydroxy-1,3-diazine-2,4-dione, hexahydro-3-hydroxy-1-methyl-1,3-diazine-2,4-dione, 3-acetoxy-hexahydro-1,3-diazine-2,4-dione, 1,3-diacetoxy-hexahydro-1,3-diazine-2,4-dione, 3-acetoxy-hexahydro-1-methyl-1,3-diazine-2,4-dione, 3-benzoyloxy-hexahydro-1,3-diazine-2,4-dione, 1,3-bis(benzoyloxy)-hexahydro-1,3-diazine-2,4-dione, 3-benzoyloxy-hexahydro-1-methyl-1,3-diazine-2,4-dione, hexahydro-1-hydroxy-1,3-diazine-2,4,6-trione, 1-acetoxy-hexahydro-1,3-diazine-2,4,6-trione, 1-benzoyloxy-hexahydro-1,3-diazine-2,4,6-trione, hexahydro-1,3-dihydroxy-1,3-diazine-2,4,6-trione, 1,3-diacetoxy-hexahydro-1,3-diazine-2,4,6-trione, 1,3-bis(benzoyloxy)-hexahydro-1,3-diazine-2,4,6-trione, 3-hydroxyuracil, 3-acetoxyuracil, 3-benzoyluracil, and other compounds having the skeleton represented by Formula (IIc); hexahydro-4-hydroxy-1,2,4-triazine-3,5-dione, hexahydro-4-hydroxy-1,2-dimethyl-1,2,4-triazine-3,5-dione, 4-acetoxy-hexahydro-1,2,4-triazine-3,5-dione, 4-acetoxy-hexahydro-1,2-dimethyl-1,2,4-triazine-3,5-dione, 4-benzoyloxy-hexahydro-1,2,4-triazine-3,5-dione, 4-benzoyloxy-hexahydro-1,2-dimethyl-1,2,4-triazine-3,5-dione, and other compounds having the skeleton represented by Formula (IId); hexahydro-1,3,5-trihydroxy-1,3,5-triazine-2,4,6-trione, 1,3,5-triacetoxy-hexahydro-1,3,5-triazine-2,4,6-trione, 1,3,5-tris(benzoyloxy)-hexahydro-1,3,5-triazine-2,4,6-trione, hexahydro-1,3,5-tris(methoxymethyloxy)-1,3,5-triazine-2,4, 6-trione, hexahydro-1-hydroxy-1,3,5-triazine-2,6-dione, hexahydro-1-hydroxy-3,5-dimethyl-1,3,5-triazine-2,6-dione, 1-acetoxy-hexahydro-1,3,5-triazine-2,6-dione, 1-acetoxy-hexahydro-3,5-dimethyl-1,3,5-triazine-2,6-dione, 1-benzoyloxy-hexahydro-1,3,5-triazine-2,6-dione, 1-benzoyloxy-hexahydro-3,5-dimethyl-1,3,5-triazine-2,6-dione, and other compounds having the skeleton represented by Formula (IIe) such as compounds represented by Formula (2); hexahydro-5-hydroxy-1,2,3,5-tetrazine-4,6-dione, hexahydro-5-hydroxy-1,2,3-trimethyl-1,2,3,5-tetrazine-4,6-dione, 5-acetoxy-hexahydro-1,2,3,5-tetrazine-4,6-dione, 5-acetoxy-hexahydro-1,2,3-trimethyl-1,2,3,5-tetrazine-4,6-dione, 5-benzoyloxy-hexahydro-1,2,3,5-tetrazine-4,6-dione, 5-benzoyloxy-hexahydro-1,2,3-trimethyl-1,2,3,5-tetrazine-4,6-dione, and other compounds having the skeleton represented by Formula (IIf).
Among the nitrogen-containing cyclic compounds, compounds wherein X is an xe2x80x94OR group and R is a hydrogen atom (N-hydroxy cyclic compounds) can be prepared according to a known procedure or a combination of such procedures. Compounds wherein X is an xe2x80x94OR group and R is a hydroxyl-protecting group can be prepared by introducing a desired protecting group into a corresponding compound wherein R is a hydrogen atom (N-hydroxy cyclic compounds) according to a conventional reaction procedure for the introduction of protecting groups.
More specifically, among the cyclic imide compounds, compounds wherein X is an xe2x80x94OR group and R is a hydrogen atom (N-hydroxy cyclic imide compounds) can be prepared by a conventional imidization process such as a process that comprises the steps of allowing a corresponding acid anhydride to react with hydroxylamine for ring-opening of an acid anhydride group, and closing the ring to form an imide. For example, N-acetoxyphthalimide can be prepared by allowing N-hydroxyphthalimide to react with acetic anhydride or to react with an acetyl halide in the presence of a base. These compounds can also be prepared by other processes.
Typically preferred imide compounds are N-hydroxysuccinimide, N-hydroxyphthalimide, N,Nxe2x80x2-dihydroxypyromellitic diimide, N-hydroxyglutarimide, N-hydroxy-1,8-naphthalenedicarboximide, N,Nxe2x80x2-dihydroxy-1,8;4,5-naphthalenetetracarboxylic diimide, and other N-hydroxyimide compounds derived from aliphatic polycarboxylic anhydrides (cyclic anhydrides) or aromatic polycarboxylic anhydrides (cyclic anhydrides); and compounds derived from the N-hydroxyimide compounds by introduction of a protecting group into a hydroxyl group thereof.
Among the cyclic acylurea compounds, for example, 1,3,5-triacetoxy-hexahydro-1,3,5-triazine-2,4,6-trione (i.e., 1,3,5-triacetoxyisocyanuric acid) can be prepared by allowing hexahydro-1,3,5-trihydroxy-1,3,5-triazine-2,4,6-trione (i.e., 1,3,5-trihydroxyisocyanuric acid) to react with acetic anhydride or to react with an acetyl halide in the presence of a base.
Among the nitrogen-containing cyclic compounds, fat-soluble compounds are preferably used as a catalyst in the process of the present invention. In this case, the catalyst can effectively act due to its high solubility even when the reaction is performed in the absence of a solvent or in a low-polarity solvent. The reaction thereby rapidly proceeds to increase productivity and to make separation and purification procedures of target products easier.
Such fat-soluble nitrogen-containing cyclic compounds include, but are not limited to, compounds represented by Formula (1) wherein X is an xe2x80x94OR group and R is a hydrogen atom; at least one of the substituents R1 to R6 and of substituents of the double bond, aromatic ring or non-aromatic ring formed by at least two of R1 to R6 with a carbon atom or carbon-carbon bond constituting the cyclic imide skeleton is a C5-C30 acyloxy group or a C5-C30 substituted oxycarbonyl group. Typical examples of these compounds are compounds represented by Formula (1a), wherein R11 and R16 are each an acyloxy group, preferably a C5-C30 aliphatic acyloxy group, alicyclic acyloxy group or aromatic acyloxy group, and more preferably a C6-C20 aliphatic acyloxy group, a cyclohexylcarbonyl group, or a benzoyloxy group, and R12 and R15 are hydrogen atoms; compounds represented by Formula (1c), wherein R18 is a substituted oxycarbonyl group, preferably a C5-C30 alkoxy-carbonyl group, a cycloalkyloxycarbonyl group, or an aryloxycarbonyl group, and more preferably a C6-C20 alkoxy-carbonyl group, a cyclohexyloxycarbonyl group, or a phenoxycarbonyl group, and R17, R19, and R20 are hydrogen atoms; compounds represented by Formula (1c), wherein R18 and R19 are each a substituted oxycarbonyl group, preferably a C5-C30 alkoxy-carbonyl group, a cycloalkyloxycarbonyl group, or an aryloxycarbonyl group, and more preferably a C6-C20 alkoxy-carbonyl group, a cyclohexyloxycarbonyl group, or a phenoxycarbonyl group, and R17 and R20 are hydrogen atoms. Examples of such fat-soluble imide compounds are compounds described as cyclic imide compounds each having a solubility parameter of less than or equal to 26 [(MPa)1/2] as determined by the Fedors"" method in European Patent Application Publication No. EP 1238704 A2. The fat-soluble nitrogen-containing cyclic compounds also include cyclic acylurea compounds represented by Formula (II) wherein R is a hydrogen atom; and at least one of Rb, Rc, and the double bond, aromatic ring, and non-aromatic ring formed by at least two of Ra, Rb, Rc, and Rd with the carbon atom, nitrogen atom, or carbon-carbon (nitrogen) bond constituting the cyclic acylurea skeleton is a C5-C30 acyloxy group or a C5-C30 substituted oxycarbonyl group.
Each of the nitrogen-containing cyclic compounds having the skeleton represented by Formula (i) as a constituent of their ring can be used alone or in combination in the reaction. For example, a cyclic imide compound having the cyclic imide skeleton of Formula (I) can be used in combination with a cyclic acylurea compound having the cyclic acylurea skeleton of Formula (II). The nitrogen-containing cyclic compound(s) can be formed in the reaction system.
The amount of the nitrogen-containing cyclic compound(s) can be selected within a broad range and is, for example, from about 0.0000001 to about 1 mole, preferably from about 0.000001 to about 0.5 mole, more preferably from about 0.00001 to about 0.4 mole, and often from about 0.0001 to about 0.35 mole per mole of the substrate [the compound (A) capable of generating a free radical (hereinafter briefly referred to as xe2x80x9cradical-formable compound (A)xe2x80x9d)]
Promoters (Co-catalysts)
Where necessary, a promoter (co-catalyst) can be used in combination with the nitrogen-containing cyclic compound catalyst. Such promoters include, but are not limited to, vanadium compounds, manganese compounds, cobalt compounds, compounds of Group 1 and Group 2 metal elements of the Periodic Table of Elements; and organic onium salts. In addition, promoters for imide compound catalysts described in, for example, Japanese Unexamined Patent Application Publication No. 09-327626 can also be used. Each of these promoters can be used alone or in combination. The reaction system may further comprise an initial activator such as a radical initiator, a radical reaction accelerator, and an oxidizing agent.
Radical-formable Compounds (A)
Radical-formable compounds (A) for use in the present invention are not specifically limited as long as they are compounds capable of generating a stable free radical. Typical examples thereof are (A1) aromatic compounds and unsaturated compounds each having a methyl group or methylene group at the adjacent position to an aromatic ring or an unsaturated bond; (A2) non-aromatic cyclic compounds constitutively having a methylene group in their ring; (A3) compounds each having a methine carbon atom; and other compounds having a hydrocarbon moiety capable of generating a free radical.
These compounds may each have at least one substituent within ranges not adversely affecting the reaction. Such substituents include, but are not limited to, alkyl groups(e.g., methyl, ethyl, isopropyl, t-butyl, and other C1-C4 alkyl groups), alkenyl groups (e.g., vinyl, allyl, and other C1-C4 alkenyl groups), alkynyl groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups (e.g., phenyl, and naphthyl groups), acyl groups, heterocyclic groups, halogen atoms, hydroxyl group, mercapto group, substituted oxy groups (e.g., methoxy, other C1-C4 alkoxy groups, and other alkoxy groups; phenoxy, and other aryloxy groups; and acetyloxy, and other acyloxy groups), substituted thio groups, carboxyl group, substituted oxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, other C1-C4 alkoxy-carbonyl, and other alkoxycarbonyl groups), substituted or unsubstituted carbamoyl groups, cyano group, nitro group, substituted or unsubstituted amino groups (e.g., amino group, N,N-dimethylamino, and other N,N-di-C1-C4 alkylamino groups), sulfo group, and groups each comprising a plurality of these groups combined with each other.
The aromatic compounds and unsaturated compounds (A1) each having a methyl group or methylene group at the adjacent position to an aromatic ring or an unsaturated bond include (A1-1) aromatic compounds each having a methyl group or methylene group at the adjacent position (a xe2x80x9cbenzyl positionxe2x80x9d) to an aromatic ring; and (A1-2) non-aromatic compounds each having a methyl group or methylene group at the adjacent position to an unsaturated bond such as a carbon-carbon unsaturated bond, and a carbon-oxygen double bond).
In the aromatic compounds (A1-1), the aromatic ring may be any of aromatic hydrocarbon rings and aromatic heterocyclic rings. Such aromatic hydrocarbon rings include, for example, benzene ring, and condensed carbon rings such as naphthalene, azulene, indacene, anthracene, phenanthrene, triphenylene, pyrene, and other condensed carbon rings each having two to ten condensed 4- to 7-membered carbon rings. The heterocyclic rings include, but are not limited to, heterocyclic rings each containing an oxygen atom as a heteroatom, such as furan, oxazole, isoxazole, and other 5-membered rings, 4-oxo-4H-pyran, and other 6-membered rings, benzofuran, isobenzofuran, 4-oxo-4H-chromene, and other condensed rings; heterocyclic rings each containing a sulfur atom as a heteroatom, such as thiophene, thiazole, isothiazole, thiadiazole, and other 5-membered rings, 4-oxo-4H-thiopyran, and other 6-membered rings, benzothiophene and other condensed rings; heterocyclic rings each containing a nitrogen atom as a heteroatom, such as pyrrole, pyrazole, imidazole, triazole, and other 5-membered rings, pyridine, pyridazine, pyrimidine, pyrazine, and other 6-membered rings, indole, quinoline, acridine, naphthyridine, quinazoline, purine, and other condensed rings.
The methylene group at the adjacent position to the aromatic ring may be a methylene group constituting a non-aromatic ring condensed to the aromatic ring. The compounds (A1-1) may each have both a methyl group and a methylene group at the adjacent position to an aromatic ring.
The aromatic compounds each having a methyl group at the adjacent position to an aromatic ring include, for example, aromatic hydrocarbons each having about one to six methyl groups substituted on an aromatic ring, such as toluene, xylene, 1-ethyl-4-methylbenzene, 1-ethyl-3-methylbenzene, 1-t-butyl-4-methylbenzene, 1-methoxy-4-methylbenzene, mesitylene, durene, methylnaphthalene, methylanthracene, and 4,4xe2x80x2-dimethylbiphenyl; and heterocyclic compounds each having about one to six methyl groups substituted on a heterocyclic ring, such as 2-methylfuran, 3-methylfuran, 3-methylthiophene, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 4-methylindole, and 2-methylquinoline.
The aromatic compounds each having a methylene group at the adjacent position to an aromatic ring include, but are not limited to, aromatic hydrocarbons each having an alkyl group or substituted alkyl group containing two or more carbon atoms, such as ethylbenzene, propylbenzene, 1,4-diethylbenzene, and diphenylmethane; aromatic heterocyclic compounds each having an alkyl group or substituted alkyl group containing 2 or more carbon atoms, such as 2-ethylfuran, 3-propylthiophene, 4-ethylpyridine, and 4-butylquinoline; and compounds each having a non-aromatic ring condensed to an aromatic ring and having a methylene group in the non-aromatic ring at the adjacent position to the aromatic ring, such as dihydronaphthalene, indene, indan, tetralin, fluorene, acenaphthene, phenalene, indanone, and xanthene.
The non-aromatic compounds (A1-2) each having a methyl group or methylene group at the adjacent position to an unsaturated bond include, but are not limited to, (A1-2a) chain unsaturated hydrocarbons each having a methyl group or methylene group at the xe2x80x9callyl positionxe2x80x9d, and (A1-2b) compounds each having a methyl group or methylene group at the adjacent position to a carbonyl group, its equivalent, a cyano group or a nitro group.
Examples of the chain unsaturated hydrocarbons (A1-2a) are propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 2-hexene, 1, 5-hexadiene, 1-octene, 3-octene, undecatriene, and other chain unsaturated hydrocarbons each containing from about 3 to about 20 carbon atoms. Examples of the compounds (A1-2b) include ketones such as acetone, methyl ethyl ketone, acetophenone, acetylacetone, acetoacetic esters, xcex1-acetyl-xcex3-butyrolactone, and other chain ketones (inclusive of ketoesters and ketolactones); cyclopentanone, cyclohexanone, cyclododecanone, and other cyclic ketones; aldehydes such as acetaldehyde, propionaldehyde, and phenylaldehyde; carboxylic acids and esters thereof, such as acetic acid, propionic acid, phenylacetic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and esters of these acids; lactones such as xcex2-propiolactone, xcex3-butyrolactone, xcex4-valerolactone, and xcex5-caprolactone; acid anhydrides such as adipic anhydride; amides such as N,N-dimethylacetamide; lactams such as xcex2-propiolactam, xcex3-butyrolactam, xcex4-valerolactam, and xcex5-caprolactam; nitriles such as acetonitrile, propionitrile, malononitrile, and ethyl cyanoacetate; imines such as N-isopropylidenebenzylamine, and N-(1-methylbutylidene)butylamine; and nitro compounds such as nitromethane, and nitroethane.
The non-aromatic cyclic compounds (A2) each constitutively having a methylene group in their ring include, for example, (A2-1) cycloalkanes, (A2-2) cycloalkenes, and (A2-3) non-aromatic heterocyclic compounds.
The cycloalkenes (A2-1) include, but are not limited to, compounds each having a 3- to 30-membered cycloalkane ring, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotetradecane, cyclohexadecane, cyclotetracosane, cyclotriacontane, and derivatives of these compounds. Preferred cycloalkane rings include 5- to 30-membered cycloalkane rings, of which 5- to 20-membered cycloalkane rings are typically preferred.
The cycloalkenes (A2-2) include, but are not limited to, compounds each having a 3- to 30-membered cycloalkene ring, such as cyclopropene, cyclobutene, cyclopentene, cyclooctene, cyclohexene, 1-methyl-cyclohexene, isophorone, cycloheptene, cyclododecene, as well as cyclopentadiene, 1,3-cyclohexadiene, 1,5-cyclooctadiene, and other cycloalkadienes, cyclooctatriene and other cycloalkatrienes, and derivatives of these compounds. Preferred cycloalkenes include compounds each having a 3- to 20-membered ring, of which compounds each having a 3- to 12-membered ring are typically preferred.
The non-aromatic heterocyclic compounds (A2-3) include, but are not limited to, 5- or 6-membered cyclic compounds each having at least one hetero atom selected from nitrogen atoms, oxygen atoms, and sulfur atoms; and condensed heterocyclic compounds each having a 5- or 6-membered ring having the hetero atom and being condensed to an aromatic ring. Examples of such compounds are dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, piperidine, piperazine, pyrrolidine, xanthene, and derivatives of these compounds.
Another ring (an aromatic or non-aromatic carbon ring or heterocyclic ring) may be condensed to the ring of the non-aromatic cyclic compounds (A2) while commonly possessing one or more atoms. In this case, a bridged ring may be formed. The compounds (A3) each having a methine carbon atom include, for example, (A3-1) cyclic compounds each having a methine group (i.e., a methine carbon-hydrogen bond) as a constitutional unit of a ring, and (A3-2) chain compounds each having a methine carbon atom.
The cyclic compounds (A3-1) include, for example, (A3-1a) bridged compounds each having at least one methine group, and (A3-1b) non-aromatic cyclic compounds (e.g., alicyclic hydrocarbons) each having a hydrocarbon group combined with their ring. The bridged compounds also include compounds, in which two rings commonly possess two carbon atoms, such as hydrogenated products of condensed polycyclic aromatic hydrocarbons.
The bridged compounds (A3-1a) include, but are not limited to, decalin, bicyclo[2.2.0]hexane, bicyclo[2.2.2]octane, bicyclo[3.2.1]octane, bicyclo[4.3.2]undecane, bicyclo[3.3.3]undecane, thujone, carane, pinane, pinene, bornane, bornylene, norbornane, norbornene, camphor, camphoric acid, camphene, tricyclene, tricyclo[5.2.1.03,8]decane, tricyclo[22.214.171.124,5]decane, exotricyclo[5.2.1.02,6]decane, endotricyclo[5.2.1.02,6]decane, tricyclo[220.127.116.11,5]undecane, tricyclo[126.96.36.199,5] undecane, endotricyclo[5.2.2.02,6]undecane, adamantane, 1-adamantanol, 1-chloroadamantane, 1-methyladamantane, 1,3-dimethyladamantane, 1-methoxyadamantane, 1-carboxyadamantane, 1-methoxycarbonyladamantane, 1-nitroadamantane, tetracyclo[22.214.171.124,5.17,10] dodecane, perhydroanthracene, perhydroacenaphthene, perhydrophenanthrene, perhydrophenalene, perhydroindene, quinuclidine, and other bridged hydrocarbons or bridged heterocyclic compounds each having two to four rings, and derivatives thereof. These bridged compounds each have a methine carbon atom at a bridgehead position (corresponding to a junction position when two rings commonly possess two atoms).
The non-aromatic cyclic compounds (A3-1b) each having a hydrocarbon group combined with their ring include, but are not limited to, 1-methylcyclopentane, 1-methylcyclohexane, limonene, menthenes, menthol, carbomenthone, menthone, and other alicyclic hydrocarbons each having from about 3 to about 15 members and having a hydrocarbon group (e.g., an alkyl group) combined with its ring, and their derivatives. The hydrocarbon group just mentioned above may contain from about 1 to about 20 carbon atoms, and preferably from about 1 to about 10 carbon atoms. The non-aromatic cyclic compounds (A3-1b) each having a hydrocarbon group combined with a ring have a methine carbon atom at the bonding position between the ring and the hydrocarbon group.
The chain compounds (open-chain compounds) (A3-2) each having a methine carbon atom include, but are not limited to, chain hydrocarbons each having a tertiary carbon atom, such as isobutane, isopentane, isohexane, 3-methylpentane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3,4-dimethylhexane, 3-methyloctane, and other aliphatic hydrocarbons each containing from about 4 to about 20 carbon atoms, and preferably from about 4 to about 10 carbon atoms, and derivatives thereof.
The compounds (A) capable of generating a free radical further include methane, ethane, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, tetradecane, octadecane, other straight-chain alkanes each containing from about 1 to about 20 carbon atoms, and other straight-chain alkanes.
Esters and Salts of Nitrous Acid (B)
At least one of esters of nitrous acid (nitrous esters) and salts of nitrous acid (nitrites) (hereinafter may briefly referred to as xe2x80x9cnitrous ester and/or nitrite (B)xe2x80x9d) is used as a reacting agent in the present invention. Each of these nitrous esters and nitrites can be used alone or in combination.
Such nitrous esters include, but are not limited to, methyl nitrite, ethyl nitrite, propyl nitrite, isopropyl nitrite, butyl nitrite, isobutyl nitrite, t-butyl nitrite, amyl nitrite, isoamyl nitrite, t-amyl nitrite, hexyl nitrite, and other alkyl nitrites; phenyl nitrite, and other aryl nitrites; benzyl nitrite, and other aralkyl nitrites. Preferred nitrous esters include C1-C6 alkyl nitrites, and other alkyl nitrites. The nitrites (nitrous acid salts) include, but are not limited to, ammonium nitrite; lithium nitrite, sodium nitrite, potassium nitrite, and other alkali metal salts of nitrous acid; magnesium nitrite, calcium nitrite, barium nitrite, and other alkaline earth metal salts of nitrous acid; zinc nitrite, and other metal salts of nitrous acid.
The nitrous ester and/or nitrite may be supplied to the reaction system as intact or in the form of a solution prepared by dissolving the nitrous ester and/or nitrite in an appropriate solvent. The nitrous ester and/or nitrite can be formed within the reaction system. For example, a corresponding nitrous ester can be formed by adding an alcohol and a nitrogen oxide such as NO and N2O3 to system, or by adding an alcohol, a metal salt of nitrous acid, and an acid to the reaction system.
Reactions
The reaction is performed in the presence of, or in the absence of, a solvent. The solvent can be any solvent that is inert under reaction conditions. Such solvents include, but are not limited to, acetic acid, propionic acid, trifluoroacetic acid, and other organic acids; acetonitrile, propionitrile, benzonitrile, and other nitrites; formamide, acetamide, dimethylformamide (DMF), dimethylacetamide, and other amides; hexane, octane, and other aliphatic hydrocarbons; chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, trifluoromethylbenzene, and other halogenated hydrocarbons; nitrobenzene, nitromethane, nitroethane, and other nitro compounds; ethyl acetate, butyl acetate, and other esters; and mixtures of these solvents. Among them, acetic acid and other organic acids, acetonitrile, benzonitrile, and other nitrites, trifluoromethylbenzene, and other halogenated hydrocarbons, ethyl acetate and other esters are often used as the solvent.
The ratio of the radical-formable compound (A) to the nitrous ester and/or nitrite (B) can appropriately be selected depending on the types (costs and reactivity) and combinations of the two compounds. For example, the radical-formable compound (A) may be used in an equivalent amount or in excess (e.g., from about 1.1 to about 50 times by equivalent or more, preferably from about 3 to 30 times by equivalent) to the nitrous ester and/or nitrite (B). Alternatively, the nitrous ester and/or nitrite (B) may be used in excess to the radical-formable compound (A).
The process of the present invention has a feature in that the reaction smoothly proceeds even under mild conditions. A reaction temperature can be appropriately selected depending on the types of the compound (A), the nitrous ester and/or nitrite (B), and the nitrogen-containing cyclic compound or the type of the target product, and is, for example, from about 0xc2x0 C. to about 250xc2x0 C., preferably from about 25xc2x0 C. to 150xc2x0 C., and more preferably from about 40xc2x0 C. to about 120xc2x0 C. The reaction may be performed in an atmosphere of an inert gas such as nitrogen gas or argon gas or in an atmosphere of the air or oxygen gas depending on the type of the target product and other conditions. The reaction can be performed at atmospheric pressure or under a pressure (under a load) according to a conventional procedure such as batch system, semi-batch system, or continuous system such as multistage continuous circulation system.
The process of the present invention produces, for example, oxime compounds each having a hydroxyimino group combined with a radical-generating site of the radical-formable compound (A) (substrate), nitro compounds each having a nitro group combined with the radical-generating site; nitrile compounds each having a nitrilo group combined with the radical-generating site, nitroso compounds having a nitroso group combined with the radical-generating site, and dimers thereof (di-N-oxide compounds having two molecules of a nitroso compound combined through their nitrogen atom), and other nitrogen-containing organic compounds (organic compounds each having a nitrogen-atom-containing group); hydroxyl compounds each having a hydroxyl group combined with the radical-generating site; carbonyl compounds each having an oxo group combined with the radical-generating site; ester compounds each having an acyloxy group combined with the radical-generating site (for example, when an organic acid such as acetic acid is used as the solvent), and other oxygen-containing organic compounds (organic compounds each having an oxygen-atom-containing group); and unsaturated compounds each having a double bond formed between the radical-generating site and the adjacent position thereto (organic compounds each having a carbon-carbon unsaturated bond-containing group).
For example, when cyclohexane is used as the substrate, cyclohexanone oxime, nitrosocyclohexanone, its dimer (nitrosocyclohexanone dimer), nitrocyclohexane, cyclohexanone, and/or cyclohexyl acetate (when acetic acid is used as the solvent) can be formed. When toluene is used as the substrate, benzaldehyde oxime, nitromethylbenzene, benzaldehyde, benzyl acetate, benzonitrile, nitrosotoluene, and/or nitrosotoluene dimer can be formed. When isopropylbenzene is used as the substrate, isopropenylbenzene, xcex1,xcex1-dimethylbenzyl alcohol, and/or (1-methyl-1-nitroethyl)benzene can be formed.
The proportions of the resulting products can be controlled by appropriately selecting reaction conditions such as the reaction temperature, reaction time, the type and amount of the catalyst, the type of the solvent, the ratio of the radical-formable compound (A) to the nitrous ester and/or nitrite (B). In general, the compounds (A1) and (A2), and other substrates having a methyl group or methylene group as the radical-generating site yield oxime compounds, nitroso compounds and dimers thereof as major products. The compounds (A3), and other substrates having a methine group as the radical-generating site yield unsaturated compounds as major products. The mechanism is probably as follows. For example, when cyclohexane is allowed to react with a nitrous ester and/or nitrite, nitrosocyclohexane is initially formed, and nitrosocyclohexane undergoes rearrangement to thereby yield cyclohexanone oxime. Some of the nitroso compounds are in reversible equilibrium with corresponding dimers (di-N-oxide compounds derived from two molecules of the nitroso compound combined through their nitrogen atom), and the equilibrium lies to the dimers. When the reaction is performed for a long time, such a nitroso compound and its dimer are formed in a trace amount in a yield of up to less than 1%. These oxime compounds and unsaturated compounds may be probably formed via nitroso compounds as intermediates.
As a preferred embodiment of the process of the present invention, the nitrous ester and/or nitrite (B) is added intermittently in plural installments or continuously to the reaction system. By this procedure, second reactions are suppressed specifically in nitroso-conversion, and thereby a nitroso compound or its dimer can be formed with a higher selectivity than the case when the nitrous ester and/or nitrite (B) is added as a single unit (by one operation). Accordingly, an oxime compound and other target products can be obtained in a high yield as a result of, for example, a subsequent rearrangement reaction.
An oxime compound can be prepared by a single step but it is preferably prepared by two steps including allowing the radical-formable compound (A) to react with the nitrous ester and/or nitrite (B) to thereby form a nitroso compound or its dimer; and converting the formed nitroso compound or its dimer into an oxime compound. This process can significantly shorten a total reaction time by adding an additive to the reaction system or by heating the reaction system in the latter converting step (a rearrangement process of the nitroso compound). More specifically, the reaction time can be shortened to one fifth to one thirtieth. By adding an additive to the reaction system or heating the reaction system, the yield of the nitroso compound and its dimer can be reduced to a trace amount or in a yield of up to less than 1%.
Such additives used herein are not specifically limited as long as they can induce rearrangement of a nitroso form to an oxime form. Acids and bases are preferably used as the additives. Such acids include, but are not limited to, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and other sulfonic acids; sulfuric acid, nitric acid, hydrogen chloride, phosphoric acids, boric acids, fuming sulfuric acid, and other mineral acids; aluminum chloride, zinc chloride, scandium triflate, and other Lewis acids; silica, alumina, zeolite, and other solid acids; phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, other polyacids, and other complex acids; and strongly acidic cationic ion exchange resins. Examples of the bases are triethylamine, and other tertiary amines, pyridine, and other nitrogen-containing heterocyclic compounds, sodium acetate, sodium methoxide, and other organic bases; sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and other inorganic bases; magnesium oxide, hydrotalcite, hydroxyapatite, and other solid bases. These additives can be added in a single unit or in plural installments. The amount of the additive(s) is, for example, from about 0.01 to about 100 parts by weight, preferably from about 0.1 to about 50 parts by weight, and more preferably from about 0.3 to about 30 parts by weight relative to 100 parts by weight of the radical-formable compound (A).
Such a rearrangement reaction using the additive is performed at a temperature of, for example, from about 40xc2x0 C. to about 120xc2x0 C., and preferably from about 50xc2x0 C. to about 100xc2x0 C. for about 5 to about 60 minutes, and preferably about 10 to about 50 minutes. The rearrangement reaction by heating is performed at a temperature of, for example, from about 120xc2x0 C. to about 250xc2x0 C., and preferably from about 150xc2x0 C. to about 200xc2x0 C. for about 0.5 to about 30 minutes, and preferably about 2 to about 15 minutes.
After the completion of the reaction, reaction products can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, and combinations of these separation means.

Process for producing organic compounds using nitrites

Abstract: wherein X is an oxygen atom or an xe2x80x94OR group, and wherein R is a hydrogen atom or a hydroxyl-protecting group. Examples of the nitrogen-containing cyclic compound are cyclic imide compounds having a cyclic imide skeleton represented by following Formula (I):

Abstract: wherein n is 0 or 1; X is an oxygen atom or an xe2x80x94OR group, and wherein R is a hydrogen atom or a hydroxyl-protecting group.


A method and system provide a surgical system including a foot pedal and at least one pressure sensor. The foot pedal has a first axis and a second axis. The first axis and the second axis intersect and are oriented at a nonzero angle. The pressure sensor(s) are coupled with the foot pedal. The pressure sensor(s) sense at least one rotation of the foot pedal around the first axis and the second axis. The pressure sensor(s) provide at least one output based on the rotation(s).

During ophthalmic surgery, a surgeon may utilize foot-operated joysticks to manipulate surgical equipment while the surgeon's hands are actively involved in performing the surgery. For example, the surgeon may move the field of view of an imaging system, move a light source or focus a microscope using the foot-operated joystick. The foot-operated joystick may take the form of four push button switches: left, right, up and down. Typically, the surgeon moves his or her foot to depress one of the switches. The surgical device moves in the direction indicated by the switch. For example, an imaging system providing a real-time image on a display may move the field of view shown on the display toward the right of the display in response to the right switch being depressed. If the surgeon depresses the left switch, the field of view may move toward the left on the display. Depressing the up or down switches moves the field of view up and down on the display. As a result, the surgeon can control surgical equipment using their feet.
Although such a foot-operated joystick allows a surgeon to operate equipment without using his hands, the surgeon's hands may not remain stable throughout the process. When moving his foot between the switches, the surgeon frequently moves his leg and upper thigh. This motion results in unwanted movement of the surgeon's hands. Consequently, the surgeon may inadvertently harm the patient's eye. Further, controlling the motion of the surgical instrument based on which switch is depressed may result in the desired location being overshot, undershot or being more difficult to reach.
Accordingly, what is needed is a mechanism for operating surgical equipment independent of and with improved stability for the surgeon's hands.


An article of submunition which is harnessed as a rotating load through the intermediary of a connecting device to the shroud lines of a parachute. The connecting device is designed as a torque or rotational moment-transmitting spreader arrangement for the radial spacing of the coupling of the shroud lines to a spin line carrying the load; whereby a coupling device is positioned between the connecting device and the spin line, in which the coupling device is constructed as a load-dependent slip coupling for the reduction of the torque which is transmitted from the spin line to the connecting device.

1. Field of the Invention
The present invention relates to an article of submunition which is harnessed as a rotating load through the intermediary of a connecting device to the shroud lines of a parachute.
2. Discussion of the Prior Art
A system of that type has become known from the disclosure of German Laid-Open Patent Appln. 23 53 566, and is employed or the deployment of submunition equipped with search heads and which rotatingly descend into a target area. This submunition is set into a rotational movement through the onflow of air produced by guide surfaces relative to the practically punctiform of the parachute shroud lines. In order to prevent the shroud lines from turning or twisting in (and thereby to cause the parachute to pull together such that it looses its braking effect and thereby brings the submunition into a steep dive), a swivel plate is arranged intermediate the shroud lines and the load. However, in actual practice, a rotational movement which is free of torque is unattainable because of the presence of unavoidable influences of friction; inasmuch as the system dimensions allow for the utilization of only a limited swivel plate diameter size, and especially after lengthier storage periods, the coefficients of friction of such a coupling become less satisfactory. Consequently, it is unavoidable that a torque will be transmitted from the rotating load to the conveyance for the shroud lines, so that these will be twisted in relative to the rotation-supportive canopy of the parachute.
In order to be able to eliminate a swivel plate construction, for parachute-load connection of the type considered herein, it is already known to provide intermediate the practically punctiform convergence or juncture of the parachute shroud lines and the actual load a lengthy connecting belt as a spin-decoupling line. A spin line of that kind is twisted prior to the deployment of the system opposite the subsequent direction of rotation for the load whereby, after the release of the rotational movement of the load relative to the braking parachute, initially this belt spin can be attenuated without transmitting of torque into the connection for the shroud lines. It depends upon the length of this belt as to how much spin encountered in the direction of rotation of the load it can thereafter still assume prior to this leading to a noticeable torque loading in the connection for the shroud lines. A lengthy spin line is; however, undersirable due to technological and kinematic reasons associated with the system, inasmuch as it would increase the period of time and the extending and unfolding of the braking parachute subsequent to the release thereof from its packing, so that the load which has been ejected from the spin stabilized deploying carrier at a high altitude would carry out an undesirably lengthy falling motion. The result would be the encountering of a correspondingly higher shock load when the braking parachute finally opens itself. On the other hand, an excessively short spin line does not permit for the implementation of a sufficiently large number of turns up to the build up of that kind of torsional moment or torque, which can lead to the twisting or turning in of the shroud lines and, resultingly, to the steep dropping or dive of the system. Hereby, consideration must also be given to the aspect that with a reducing parachute strength; in effect, at a reducing sinking speed, that the counter-torque which is obtained through the articulation with the shroud lines (hereinafter referred to as shroud lines-torque), will reduce itself, as a consequence of which there is an increase in the danger of the twisting or turning in of the shroud lines due to the torsional moment or torque which is exerted by the spin line. When, there is then additionally separated the load; for instance, in the sense that a parachute cassette together with the braking parachute is blown off from the submunition, and thereby a rotational parachute has been freed on the submunition, this represents a sudden-like additional reduction in the strength of the braking parachute. The turning in of the parachute shroud lines then has, as a consequence, a greater sinking speed of the blown off load constituent, so that this can drop backwards into the rotational parachute for the submunition, and can thereby set the system out of function.


A communication hub for providing call tones in a communication network proximate the calling device. The communication hub comprises an interface coupled to a processor and a tone generator. The tone generator is configured to generate call tones. The processor is configured to process an in-band call tone request message to direct the tone generator to provide the call tones to a call device. The interface is configured to receive the call tone request message and provide the call tones to the call device.

Not applicable
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1. Field of the Invention
The invention relates to communication networks, and specifically, to a method and system for providing call tones in communication networks.
2. Description of the Prior Art
Call tones are generated in communication networks to provide callers with feedback regarding the status of calls and call connections. Examples of specific call tones include a dial tone, a ringback tone, a busy signal tone, and a reorder tone. The reorder tone is sometimes referred to as a fast busy signal in the art. Typically, call tones are provided in communication networks by a terminating communication device upon completion of the call connection. In some applications however, call tones can be provided by an originating communication device by triggering the call tone generation using a control or signaling channel.
FIG. 1 illustrates an example of call tone control and generation for a call session in the PSTN. On FIG. 1 the calling party removes the receiver from the calling party""s telephone 100. The originating switch 101 detects the off-hook and provides a dial tone to the calling party""s telephone 100. Responsive to receiving the dial tone, the user enters the digits for a call destination. The originating switch 101 processes the entered digits and provides a call setup message to the network 102. The network 102 provides the call setup message to the terminating switch 103 and reserves a connection between the originating switch 101 and the terminating switch 103. In response to receiving the call setup message, the terminating switch 103 provides an acknowledgment message to the network 102. If the terminating switch 103 detects the called party""s telephone 104 is off-hook or busy, the terminating switch 103 provides busy signal tones over the network 102 to the calling party""s telephone 100. If the terminating switch 103 does not detect that the called party""s telephone 104 is off-hook or busy, the terminating switch 103 provides ringback tones over the network 102 to the calling party""s telephone 100. The terminating switch 103 also rings the called party""s telephone 104 to announce the incoming call.
FIG. 2 illustrates another example of call tone generation and control for a call session in a packet communication network. On FIG. 2 the calling party removes the receiver from the calling party""s telephone 200. The originating communication hub 201 detects the off-hook event and provides an off-hook message to the network 202. Responsive to receiving the off-hook message, the network 202 provides a dial tone to the calling party""s telephone 200 via the originating communication hub 201. Responsive to receiving the dial tone the user enters the digits for the call destination. The originating communication hub 201 detects the digits and provides the digits to the network 202. The network 202 processes the digits and generates a setup message for a terminating communication hub 203 connected to the called party""s telephone 204. Responsive to receiving the setup message, the terminating communication hub 203 provides a setup acknowledgment message to the network 202. If the called party""s telephone 204 is off-hook or busy, the terminating communication hub 203 provides busy signal tones over the network 202 and communication hub 201 to the calling party""s telephone 200. If the terminating communication hub 203 does not detect the called party""s telephone 203 is off-hook or busy, the terminating communication hub 203 provides ringback tones over the network 202 and communication hub 201 to the calling party""s telephone 200. The terminating communication hub 203 also rings the called party""s telephone 204 to announce the incoming call.
It is a problem in packet communication networks to provide call tones over the network from the terminating device. The communication path between the communication hub and the network includes a limited bandwidth capacity. Unfortunately, effective call tone generation is not supported because new services such as call waiting, call forwarding, and three-way-calling have increased network bandwidth demands. Therefore, a need exists in the art to free bandwidth currently utilized by call tone generation and control in packet communication networks.
The present invention advances the art by providing a communication hub that provides call tones in communication networks at points proximate the calling device. Advantageously, bandwidth required for call completion in the communication network is significantly reduced because call tones are provided proximate the calling device using in-band call tone messaging. Also advantageously, the in-band call tone messaging could also serve as a validation that the bearer channel is functioning properly before call completion. Thus, service assurance is provided before call completion and early detection of network failures is realized. Some examples of call tones that could be provided include without limitation, ringback tones, busy signal tones, and reorder tones.
The communication hub is comprised of an interface coupled to a processor and a tone generator. The tone generator is configured to generate the call tones under control of the processor. The processor is configured to process an in-band call tone request message to direct the tone generator to provide the call tones to a call device. The interface is configured to receive the call tone request message and transmit the call tones to the call device.
In the context of the present invention the first, second, third, fourth, etc. connotations used to reference the messages, the calls, and the devices are used for the purpose of differentiating between different messages, different calls, and different devices and are not used to indicate a message sequence, call sequence or processing sequence. Also in the context of the present invention, an on-network call session is defined as a call session between two devices connected to the same communication network. An off-network to on-network call session and an on-network to off-network call session are defined as an incoming call session or an outgoing call session, respectively, between two devices connected to different communication networks. For example, an incoming call session or an outgoing call session between a call device connected to a packet network and a call device connected to the PSTN. In-band is defined as using the bearer portion of a communication path, for example, over the bearer channel in an asynchronous transfer mode (ATM) connection. Those skilled in the art will appreciate that in some environments, such as an Internet Protocol (IP) environment, in-band could simply be a pair of addresses, such as the address of the originating device and the address of the terminating device.


An early-strength polycarboxylate superplasticizer with an MOF structure and a preparation method thereof are provided. The preparation method includes the following steps: 1) performing an amidation reaction on amine-containing nanocrystalline MOFs and a halogen acyl halide organic molecule to form the halogen-containing ATRP initiator; 2) performing an ATRP reaction on the obtained ATRP initiator, an unsaturated ester monomer, an unsaturated polyether macromonomer and a transition metal complex to obtain the early-strength polycarboxylate superplasticizer with the MOF structure. The present invention regulates the number and length of branch chains and product performance by controlling the number of amine groups contained in the nanocrystalline MOFs and ATRP, and has the advantages of rapid reaction, high efficiency, non-toxic and non-pollution, and simple operation. The prepared early-strength polycarboxylate superplasticizer with the MOF structure has early-strength performance and stable product performance.

Metal-organic frameworks (MOFs) are a new kind of porous materials with infinite network structure, which is formed by rigid organic ligands bridging metal ions or metal clusters via coordination bonds. Currently, MOFs have attracted extensive attention from domestic and foreign researchers. MOFs are widely used in the fields of gas adsorption and storage, catalysis, photoelectric materials, sensing, and medical diagnosis because they possess the following advantages. MOFs enable easy accessibility to raw materials, high porosity, high specific surface area, adjustable morphology and size, rich and diverse structures, and can be prepared by various simple synthesis strategies and used for various chemical modifications according to the experimental requirements.
Polycarboxylate superplasticizers have a comb-type molecular structure, and have the advantages of good adaptability with cementitious materials, low dosage, free pollution, low cost, high water-reducing ratio, excellent slump retention, controllable setting time, low shrinkage, good appearance quality of concrete, low alkali content and low chloride ion content. MOFs generally provide significantly high porosity, and therefore provide enough space for the addition of functional groups, which makes MOFs a potential candidate for surface modification.

Early-strength polycarboxylate superplasticizer with MOF structure and preparation method thereof


A helical auger member for transporting toner in an image forming apparatus. The auger member may be implemented as part of a waste toner removal system for removing toner from a photoconductive member of a toner cartridge. Toner that is removed by a cleaner member is transported through a cleaner housing with a helical member, such as a coil wire, having a pitch to outer diameter ratio from about 1.5 to 2.5.

During the image forming process, toner is transferred from toner carrying members to print or copy media. Inefficiencies in the transfer process cause residual toner to remain on the toner carrying members or other transport members, such as transport belts, intermediate transfer belts/drums, and photoconductive members. Residual toner may also be created during registration, color calibration, paper jams, and over-print situations. This residual toner should be cleaned before it affects the quality of subsequent images. The residual or waste toner is commonly removed by a blade or other means and the removed toner is stored in a waste toner container.
Space constraints often require that a waste toner container in an electrophotographic device be located at some remote location away from the cleaning location. Because of this separation, waste toner is conveyed from the cleaning location to the waste container. The conveyance path between the cleaner location and the waste toner container is also limited by space and often travels through the internals of the electrophotographic device. Consequently, the conveyance mechanism that transports waste toner from the cleaner location to the waste toner should be designed to fit in confined spaces. On the other hand, the conveyance mechanism should be designed to transport a sufficient volume of waste toner to keep the cleaner location free of accumulated waste toner. If waste toner is not transported away from the cleaner location efficiently enough, toner may begin to accumulate and degrade the cleaning operation, resulting in poor image quality.

Auger for use in an image forming device


An airbag cover main body portion is provided including a plate-shaped opening portion, a flat portion provided to at least a region further on an inner peripheral side than the opening portion, and a plurality of welding auxiliary ribs that is provided to protrude from a region further on an outer peripheral side than the opening portion and maintain a flatness of a surface of the opening portion, wherein: a frame-shaped body includes a flap portion that tears and deploys by pressure imparted by an inflation load, ribs to be welded that are provided at least to the flap portion, facing the flat portion, and a plurality of auxiliary ribs to be welded; and the ribs to be welded and the flat portion as well as the auxiliary ribs to be welded and the welding auxiliary ribs are respectively joined by vibration welding while respectively in contact with each other.

A passenger airbag apparatus that restrains a passenger is provided in an instrument panel of a vehicle. The passenger airbag apparatus secures in place an airbag cover provided as a portion of the outer appearance of the instrument panel and a frame-shaped body that uses a rear surface of the airbag cover as an installation surface; the frame-shaped body is then fitted with components including a retainer, airbag, and inflator. When the frame-shaped body is fixed to the rear surface side of the instrument panel, the frame-shaped body is often welded using a welding technique (such as vibration welding) since these components are made of resin (see JP, A, 2008-114747, for example).
In recent years, the instrument panel of a vehicle has sometimes been designed with an outer appearance that has an overall curved surface shape. This is in response to various factors, including the design perspective, vehicle interior layout restrictions, and to ensure various functionalities. In such a case, in locations where this curved surface shape hinders vibration operations related to vibration welding, there has been high demand to devise a structure that is conducive to vibration welding, making it possible to evenly join the areas where the airbag cover main body portion and frame-shaped body face each other. According to the above prior art, a plurality of ribs is provided to the rear surface side of the instrument panel so as to extend across the entire opening portion of the airbag cover that tears open on a tear line, making it possible to evenly join these ribs and the installation surface of the frame-shaped body facing these ribs.
The instrument panel comprises an opening portion of a plate shape that is divided by a tear line for tearing. This opening portion tears open on the tear line by the pressure imparted by the inflation load of the airbag, deploying toward the occupant. According to the above prior art, the plurality of ribs is mainly provided to the rear surface of the opening portion.


A secondary battery includes a container an electrode assembly mounted in the container having a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and a cap assembly fixed to the container to seal the container. The cap assembly includes a cap plate having a terminal, a current breaker electrically connected to the cap plate; and a vent plate having a safety vent electrically connected to the current breaker, the shape of the vent plate being altered by the internal pressure of the secondary battery to alter the shape of the current breaker, and the current breaker cutting off the current path of the cap assembly.

1. Technical Field
The present invention relates to a secondary battery, and more particularly, to a cap assembly of the secondary battery.
2. Description of the Related Art
A secondary battery is a rechargeable battery that can be made into a small size or a high power. Common types of secondary batteries include the nickel-hydrogen battery, the lithium battery and the lithium-ion battery. The lithium-ion secondary battery can have a various shape, for example, square and cylindrical batteries.
For the lithium-ion battery, when it is excessively charged or its positive electrode and negative electrode are short-circuited, the electrolyte with lithium salt and organic solvent is electrolyzed at the positive electrode and the lithium metal is extracted at the negative electrode, and thereby the deterioration of the battery characteristics and the short-circuit occur. In particular, excessive charge generates excessive current, which damages an apparatus using the battery as a power source. Moreover, excessive charge generates gas to increase the internal pressure, which may cause explosion and ignition of the battery.
In an effort to overcome these difficulties, the lithium-ion battery generally has a safety device thereinside, such as a shut-down separator, a PTC device to cutoff current when the temperature increases, and a safety vent to discharge the pressure when the internal pressure increases.
For example, U.S. Pat. No. 5,985,478 entitled Pressure responsive cap assembly for rectangular battery to Kim, and issued on Nov. 16, 1999, discloses a safety device in which a through-hole formed on the negative electrode is simply riveted by use of a rivet connected to a tab while an insulator and a gasket are disposed over and below the negative electrode.
However, the above structure has a limit to increasing sealing capacity, and in particular, since the secondary battery generates a large amount of gas from the inside, it has a problem that the sealing capacity of the through-hole decreases relatively.
Japanese Patent Laid-open No. 11-219692 discloses a thin metal plate to seal a hole of a cap plate. However, this structure has a problem in that there occurs a crack in a safety vent when the external physical impact is loaded.
Moreover, if the secondary battery used as a power source for an electronic device generates excessive current, the excessive current is transmitted to the electronic device to thereby damage the electronic device. Especially, such problems are more serious to the battery for a motor driven device which repeats the charge and discharge within a short time.
Accordingly, there is a need for a safety device which can prevent the explosion and cutoff excessive current when it occurs.

Cap assembly and secondary battery with same


An apparatus for welding a plastic component to a body's aperture includes a first heating head mounted to a frame element for heating the component, a gripper for gripping the component and for mounting the component to the body's aperture, a heater arm having a second heating head mounted thereto for heating the aperture, and an actuator for mounting both the heater arm and the gripper to the frame element for alternating between a heating position wherein ia) the gripper is generally aligned with the first heating head for abutment therewith, while ib) the second heating head is positioned for heating the aperture, and a work position wherein ii) the gripper is generally aligned with the aperture for mounting the component to the aperture for welding therewith: The gripper is mounted to the actuator via a cylinder arm provided with a collision monitor to detect inadvertent collision.

Robot tools for welding a plastic part to the aperture of a gas tank are already known in the art. Such tools include a first heater to heat the plastic part, a second heater to heat the gas tank around its aperture, and gripper means for positioning the part within the aperture for a certain time during welding to allow its securing to the tank.
A drawback of such robot tools from the prior art is that misalignment of the plastic part during welding or during any other steps of the overall welding process might yield a resulting defective gas tank. At best, these defective gas tanks can be detected during a post-production visual inspection which of course takes additional time, is costly and is often unreliable.

Apparatus for welding a plastic component to the aperture of a plastic body


A control apparatus for a vehicle drive-force transmitting apparatus including a gear mechanism and a continuously-variable transmission mechanism provided in respective first and second drive-force transmitting paths. The control apparatus sets a target gear ratio of the continuously-variable transmission mechanism during a switching control operation that is executed to switch between (i) a first state in which the first drive-force transmitting path is established and (ii) a second state in which the second drive-force transmitting path is established, such that, when drive wheels are not being slipped, the target gear ratio is set to a highest gear ratio of the continuously-variable transmission mechanism, and such that, when the drive wheels are being slipped, the target gear ratio is set to an actual gear ratio at a point of time at which the drive wheels start being slipped.

There is known a control apparatus for a drive-force transmitting apparatus that is to be provided in a vehicle having a drive force source and drive wheels, wherein the drive-force transmitting apparatus includes: an input rotary member to which a drive force is to be transmitted from the drive force source; an output rotary member from which the drive force is to be outputted to the drive wheels; a gear mechanism configured to provide at least one gear ratio; and a continuously-variable transmission mechanism including a primary pulley, a secondary pulley and a transfer element looped over the primary and secondary pulleys. The drive-force transmitting apparatus defines a plurality of drive-force transmitting paths that are provided in parallel with each other between the input rotary member and the output rotary member. The plurality of drive-force transmitting paths include a first drive-force transmitting path through which the drive force is to be transmitted by the gear mechanism and a second drive-force transmitting path through which the drive force is to be transmitted by the continuously-variable transmission mechanism. WO2014/170960 discloses such a control apparatus for a vehicle having the drive-force transmitting apparatus in which the gear mechanism and a continuously-variable transmission mechanism are provided to be parallel with each other, teaching that the continuously-variable transmission mechanism provides a continuously-variable gear ratio that is lower than a gear ratio provided by the gear mechanism and that the control apparatus executes a switching control operation and a shifting control operation concurrently with each other, wherein the switching control operation is an operation for switching an operation state of the drive-force transmitting apparatus from a first state in which the first drive-force transmitting path is established to a second state in which the second drive-force transmitting path is established, while the shifting control operation is an operation for changing the gear ratio of the continuously-variable transmission mechanism. It is noted that the term "gear ratio" is defined as "rotational speed of input-side rotary member/rotational speed of output-side rotary member". For example, the gear ratio of the drive-force transmitting apparatus is defined as "rotational speed of the input rotary member/rotational speed of the output rotary member", and the gear ratio of the continuously-variable transmission is defined as "rotational speed of the primary pulley/rotational speed of the secondary pulley". It is also noted that the above-described expression that the continuously-variable gear ratio of the continuously-variable transmission mechanism is lower than the gear ratio provided by the gear mechanism, is interpreted to mean that the continuously-variable gear ratio of the continuously-variable transmission mechanism makes a vehicle running speed higher than the gear ratio of the gear mechanism, and that the highest gear ratio value of the continuously-variable gear ratio of the continuously-variable transmission mechanism can be expressed also as a lowest-speed gear ratio.

Control apparatus for vehicle drive-force transmitting apparatus


An apparatus for LED string short circuit detection constituted of: a constant current drive circuit; a plurality of LED strings, a first end of each of the plurality of LED strings coupled to a common output of the constant current drive circuit; a first sense resistor coupled between a second end of each of the plurality of LED strings and a chassis; a second sense resistor coupled between the chassis and a return of the constant current drive circuit; and a comparing circuit arranged to compare the amount of current flow through the first sense resistor with amount of current flow through the second sense resistor, the comparing circuit arranged to assert a fault signal in the event that the amount of current flow through the second sense resistor exceeds the current flow through the first sense resistor by a predetermined minimum value.

The present invention relates to the field of solid state lighting, and in particular to an arrangement driving one or more LED strings wherein a short circuit to ground is detected and driving is interrupted.
Light emitting diodes (LEDs), and in particular high intensity and medium intensity LED strings, are rapidly coming into wide use for lighting applications. LEDs with an overall high luminance are useful in a number of applications including backlighting for liquid crystal display (LCD) based monitors and televisions, collectively hereinafter referred to as a matrix display, as well as for general lighting applications.
In a large LCD matrix display, and in large solid state lighting applications, such as street lighting and signage, the LEDs are typically supplied in a plurality of strings of serially connected LEDs, the strings connected to a power source in parallel at least in part so that in the event of failure of one string at least some light is still output. The constituent LEDs of each LED string thus share a common current.
Similarly LED based lighting, also known as solid state lighting, is favored due to its high efficiency, long life, mechanical compactness and robustness, and low voltage operation. Because of the limited power capacity of a single LED device, in most applications multiple LED's are connected in series to form an LED string, wherein all of the constituent LEDs share a common current. Furthermore, as described above, multiple LED strings are typically provided either in parallel, or separately driven, to produce the desired overall light intensity.
LED strings exhibit a particular voltage to current relationship, wherein for a voltage below a minimum operating voltage no appreciable current flows, and for voltages exceeding the minimum operating voltage the current follows an exponential curve responsive to the voltage. As a result, driving of LED strings is typically performed by a constant current source, i.e. a driver which produces a fixed output current irrespective of the voltage developed across the load. Such a constant current source can be of a linear type or of a switching type, wherein the LED current is maintained at a constant pre-determined level with a control mechanism.
In practical mass production of such a multiple LED string lighting apparatus, and especially in display backlight applications, there is a possibility that at some point a LED string is shorted to a metal chassis. Such a short circuit would cause an electronic device failure or a safety hazard when electrical power is applied to the system. The constant current source will continue to drive the designed current through the normal LED strings, with the current of the shorted string bypassing the sense element, and thus not being part of the control feedback loop. Such a situation is dangerous but cannot be detected by the normal sense feedback, which is arranged to ensure that current through the sense element meets a pre-determined target. Thus, the loop of the prior art leads to a hazardous situation in the event of such a short circuit.

Method and apparatus for LED string short circuit detection and protection