US4317907A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for producing 7-(substituted)amino-3-substituted thiomethyl cephem carboxylic acids
Assignee: Toyama Chemical Co Ltd
•
Filing: 1978-02-02
•
Granted: 1982-03-02
•
Expires: 1998-02-02
Abstract
Abstract This disclosure relates to a novel process for producing 7-(substituted)amino-3-substituted thiomethyl cephem carboxylic acids which are intermediate products of cephalosporins being valuable antibacterial compounds for use in mammals including man.
Inventors
- 👤 Isamu Saikawa
- 👤 Shuntaro Takano
- 👤 Kaishu Momonoi
- 👤 Isamu Takakura
- 👤 Seietsu Kuroda
- 👤 Kiyoshi Tanaka
- 👤 Kenshin Hayashi
- 👤 Bunei Nagahashi
- 👤 Chiaki Kutani
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 18:33
CPC Classifications
C; C07; C07D; C07D501/00; C07D501/02; C07D501/04
Claims Analysis
Total Claims: 89
Claim 1
Independent Claim
305 words
A process for producing a 7-(substituted)amino-3-substituted thiomethyl cephem carboxylic acid represented by the formula: ##STR17## wherein R 1 is a hydrogen atom or C 1-4 alkyloxy group; R 2 is an amino group or a protected amino group represented by the formula ##STR18## in which R 3 , R 4 and R 5 , which may be identical or different, are hydrogen atoms or conventional cephalosporin substituents which do not participate in the reaction, or the formula ##STR19## in which R 6 and R 7 , which may be identical or different, are hydrogen atoms or conventional cephalosporin substituents which do not participate in the reaction; and R 8 is a moiety of a compound of the formula HSR 8 wherein SR 8 is a conventional 3-position cephalosporin thio substituent, or said compound (I) in which the carboxyl group is protected by a conventional cephalosporin carboxy protecting group or a conventional cephalosporin salt thereof, which comprises reacting a cephalosporanic acid represented by the formula: ##STR20## wherein R 1 and R 2 have the same meanings as defined above; X is carboxylic acyloxy or carbamoyloxy groups or one of said groups substituted by a conventional cephalosporin substituent; >Y is >S or >S→O; or said compound (II) in which the carboxyl group is protected by a conventional cephalosporin carboxy protective group or a conventional cephalosporin salt thereof with a thiol compound represented by the formula, R.sup.8 --SH (III) wherein R 8 has the same meaning as defined above, or a salt thereof with a compound forming a conventional cephalosporin salt, in a non-aqueous organic solvent at a temperature of -20° to 80° C. in the presence of boron trifluoride or a complex compound thereof which acts as boron trifluoride, the boron and the fluorine bonded to boron in said complex compound being present as BF 3 .
Claim 2
Dependent Claim
305 words
A process for producing a 7-(substituted)amino-3-substituted thiomethyl cephem carboxylic acid represented by the formula: ##STR17## wherein R 1 is a hydrogen atom or C 1-4 alkyloxy group; R 2 is an amino group or a protected amino group represented by the formula ##STR18## in which R 3 , R 4 and R 5 , which may be identical or different, are hydrogen atoms or conventional cephalosporin substituents which do not participate in the reaction, or the formula ##STR19## in which R 6 and R 7 , which may be identical or different, are hydrogen atoms or conventional cephalosporin substituents which do not participate in the reaction; and R 8 is a moiety of a compound of the formula HSR 8 wherein SR 8 is a conventional 3-position cephalosporin thio substituent, or said compound (I) in which the carboxyl group is protected by a conventional cephalosporin carboxy protecting group or a conventional cephalosporin salt thereof, which comprises reacting a cephalosporanic acid represented by the formula: ##STR20## wherein R 1 and R 2 have the same meanings as defined above; X is carboxylic acyloxy or carbamoyloxy groups or one of said groups substituted by a conventional cephalosporin substituent; >Y is >S or >S→O; or said compound (II) in which the carboxyl group is protected by a conventional cephalosporin carboxy protective group or a conventional cephalosporin salt thereof with a thiol compound represented by the formula, R.sup.8 --SH (III) wherein R 8 has the same meaning as defined above, or a salt thereof with a compound forming a conventional cephalosporin salt, in a non-aqueous organic solvent at a temperature of -20° to 80° C. in the presence of boron trifluoride or a complex compound thereof which acts as boron trifluoride, the boron and the fluorine bonded to boron in said complex compound being present as BF 3 .
Claim 3
Dependent Claim
13 words
The process according to claim 1, wherein R 2 is an amino group.
Claim 4
Dependent Claim
36 words
The process according to claim 1, wherein R 2 is a group represented by the formula ##STR21## in which R 3 , R 4 and R 5 have the same meaning as defined in claim 1.
Claim 5
Dependent Claim
33 words
The process according to claim 1, wherein R 2 is a group represented by the formula ##STR22## in which R 6 and R 7 have the same meanings as defined in claim 1.
Claim 6
Dependent Claim
21 words
The process according to claim 1, wherein the starting compound is a salt of the compound represented by the formula (II).
Claim 7
Dependent Claim
28 words
The process according to claim 5, wherein the salt of the compound represented by the formula (II) is a salt at an acidic group of the compound II.
Claim 8
Dependent Claim
28 words
The process according to claim 5, wherein the salt of the compound represented by the formula (II) is a salt at a basic group of the compound (II).
Claim 9
Dependent Claim
14 words
The process according to claim 6, wherein the salt is an alkali metal salt.
Claim 10
Dependent Claim
12 words
The process according to claim 8, wherein the alkali metal is sodium.
Claim 11
Dependent Claim
19 words
The process according to claim 7, wherein the salt is a mineral acid salt or a sulfonic acid salt.
Claim 12
Dependent Claim
16 words
The process according to claim 10, wherein the mineral acid salt is a hydrochloric acid salt.
Claim 13
Dependent Claim
16 words
The process according to claim 10, wherein the sulfonic acid salt is a p-toluenesulfonic acid salt.
Claim 14
Dependent Claim
21 words
The process according to claim 1, wherein the starting compound is an ester of the compound represented by the formula (II).
Claim 15
Dependent Claim
10 words
The process according to claim 1, wherein >Y is >S.
Claim 16
Dependent Claim
10 words
The process according to claim 1, wherein >Y is >S→O.
Claim 17
Dependent Claim
13 words
The process according to claim 1, wherein R 1 is a hydrogen atom.
Claim 18
Dependent Claim
15 words
The process according to claim 1, wherein R 1 is a C 1-4 alkyloxy group.
Claim 19
Dependent Claim
13 words
The process according to claim 17, wherein R 1 is a methoxy group.
Claim 20
Dependent Claim
14 words
The process according to claim 1, wherein X is a C 1-8 acyloxy group.
Claim 21
Dependent Claim
14 words
The process according to claim 19, wherein X is a C 1-8 alkanoyloxy group.
Claim 22
Dependent Claim
10 words
The process according to claim 20, wherein X is acetoxy.
Claim 23
Dependent Claim
64 words
The process according to claim 3, wherein R 3 , R 4 and R 5 , which may be identical or different, are unsubstituted or substituted C 1-5 alkyl, C 2-4 alkenyl, C 5-7 cycloalkyl, C 5-7 cycloalkenyl, aryl, aralkyl, ring carbon containing heterocyclic containing O, N and S atoms alone or in any combination in any position of the ring, or carboxylic acyl.
Claim 24
Dependent Claim
63 words
The process according to claim 4, wherein R 6 and R 7 , which may be identical or different, are hydrogen, unsubstituted or substituted C 1-5 alkyl, C 2-4 alkenyl, C 5-7 cycloalkyl, C 5-7 cycloalkenyl, aryl, aralkyl, ring carbon containing heterocyclic containing O, N and S atoms alone or in any combination in any position of the ring, or carboxylic acyl hydrocarbon.
Claim 25
Dependent Claim
26 words
The process according to claim 23, wherein R 6 and R 7 are different from each other and represent hydrogen or unsubstituted or substituted aryl hydrocarbon.
Claim 26
Dependent Claim
18 words
The process according to claim 24, wherein R 6 is hydrogen, and R 7 is 2-hydroxyphenyl or 3,5-di-tert.-butyl-4-hydroxyphenyl.
Claim 27
Dependent Claim
26 words
The process according to claim 1, wherein the organic solvent is a nitrile, a nitroalkane, an organic carboxylic acid, a ketone, an ether or a sulfolane.
Claim 28
Dependent Claim
22 words
The process according to claim 1, wherein the reaction is effeced in the presence of a dehydrating agent to maintain anhydrous conditions.
Claim 29
Dependent Claim
17 words
The process according to claim 1, wherein the reaction is effected in the presence of boron trifluoride.
Claim 30
Dependent Claim
20 words
The process according to claim 1, wherein the reaction is effected in the presence of a boron trifluoride complex compound.
Claim 31
Dependent Claim
35 words
The process according to claim 29, wherein the boron trifluoride complex compound is a dialkyl ether complex, an amine complex, an aliphatic acid complex, a nitrile complex, a carboxylic ester complex, or a phenol complex.
Claim 32
Dependent Claim
25 words
The process according to claim 30, wherein the boron trifluoride complex compound is a dialkyl ether complex, an aliphatic acid complex, or a nitrile complex.
Claim 33
Dependent Claim
32 words
The process according to claim 1, wherein R 8 is an unsubstituted or substituted alkyl, cycloalkyl, aryl hydrocarbon, aralkyl, carboxylic acyl, thiocarbamoyl, alkoxythiocarbonyl, aryloxythiocarbonyl, cycloalkyloxythiocarbonyl, amidino or ring carbon containing heterocyclic group.
Claim 34
Dependent Claim
40 words
The process according to claim 32, wherein R 8 is an unsubstituted or substituted C 1-8 alkyl, aryl or nitrogen-containing ring carbon containing heterocyclic group, said heterocyclic group containing at least one nitrogen atom with or without oxygen or sulfur.
Claim 35
Dependent Claim
18 words
The process according to claim 33, wherein R 8 is an unsubstituted or substituted C 1-8 alkyl group.
Claim 36
Dependent Claim
33 words
The process according to claim 33, wherein R 8 is an unsubstituted or substituted nitrogen-containing ring carbon containing heterocyclic group which contains at least one nitrogen atom with or without oxygen or sulfur.
Claim 37
Dependent Claim
49 words
The process according to claim 35, wherein R 8 is an unsubstituted or substituted tetrazolyl, thiadiazolyl, triazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolyl, indolyl, indazolyl, oxadiazolyl, thiadiazolyl, thiatriazolyl, triazinyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, triazolopyridyl, purinyl, pyridine-1-oxide-2-yl, pyridazine-1-xide-6-yl, tetrazolopyridazinyl, tetrazolopyrimidinyl, thiazolopyridazinyl, thiadiazolopyridazinyl or triazolopyrimidinyl.
Claim 38
Dependent Claim
18 words
The process according to claim 36, wherein R 8 is an unsubstituted or substituted tetrazolyl, thiadiazolyl, or triazolyl.
Claim 39
Dependent Claim
21 words
The process according to claim 37, wherein R 8 is 2-(5-methyl-1,3,4-thiadiazolyl), 2-(1,3,4-thiadiazolyl), 2-(1-methyl-1,3,4-triazolyl), 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-vinyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl]or 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl].
Claim 40
Dependent Claim
30 words
The process according to claim 2, wherein R 1 is a hydrogen atom and R 8 is an unsubstituted or substituted alkyl, aryl hydrocarbon or ring carbon containing heterocyclic group.
Claim 41
Dependent Claim
30 words
The process according to claim 39, wherein R 8 is an unsubstituted or substituted nitrogen-containing heterocyclic group which contains at least one nitrogen atom with or without oxygen or sulfur.
Claim 42
Dependent Claim
48 words
The process according to claim 40, wherein R 8 is unsubstituted or substituted tetrazolyl, thiadiazolyl, triazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, quinazolyl, indolyl, indazolyl, oxadiazolyl, thiadiazolyl, thiatriazolyl, triazinyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, triazolopyridyl, purinyl, pyridine-1-oxide-2-yl, pyridazine-1-oxide-6-yl, tetrazolopyridazinyl, tetrazolopyrimidinyl, thiazolopyridazinyl, thiadiazolopyridazinyl or triazolopyrimidinyl.
Claim 43
Dependent Claim
53 words
The process according to claim 39, wherein R 8 is n-propyl, carboxymethyl, ethoxycarbonylmethyl, phenyl, 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-ethyl-1,2,3,4-tetrazolyl), 5-(1-sulfomethyl-1,2,3,4-tetrazolyl), 5-(1-carboxymethyl-1,2,3,4-tetrazolyl), 5-[2-(2-carbamoyletyl)-1,2,3,4-tetrazolyl], 5-[1-(2-sulfamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-diethylaminoethyl)-1,2,3,4-tetrazolyl], 5-(1-methoxycarbonylmethyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-(1-phenyl-1,2,3,4-tetrazolyl), 5-(1-vinyl-1,2,3,4-tetrazolyl), 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(5-ethyl-1,3,4-thiadiazolyl), 2-(5-amino-1,3,4-thiadiazolyl), 2-(5-phenyl-1,3,4-thiadiazolyl), 5-(3-methyl-1,2,4-thiadiazolyl), 2-(5-carboxymethyl-1,3,4-thiadiazolyl), 5-(1,2,3-triazolyl), 2-(1-methyl-1,3,4-triazolyl), 2-(5-methyl-1,3,4-triazolyl), 2-(1,5-dimethyl-1,3,4-triazolyl), 4-(5-ethoxycarbonyl-1,2,3-triazolyl), 4-(5-carboxyl-1,2,3-triazolyl), 2-(5-ethoxycarbonylmethyl-1,3,4-triazolyl), benzoxazolyl, 2-(benzimidazolyl), 2-(5-methyl-1,3,4-oxadiazolyl), 2-(5-methyl-1,3-thiazolyl), 2-(5-methyl-1,3-oxazolyl), 2-(1,3-thiazolyl), 5-(1,2,3,4-thiatriazolyl) or 2-(imidazolyl).
Claim 44
Dependent Claim
22 words
The process according to claim 42, wherein R 8 is 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(1-methyl-1,3,4-triazolyl), 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-vinyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], or 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl].
Claim 45
Dependent Claim
23 words
The process according to claim 42, wherein the objective compound is a compound represented by the formula (I) set forth in claim 1.
Claim 46
Dependent Claim
33 words
The process according to claim 42, wherein a compound represented by the formula (II) set forth in claim 1 wherein >Y is >S and X is acetoxy is used as the starting compound.
Claim 47
Dependent Claim
34 words
The process according to claim 1, wherein R 1 is a hydrogen atom, R 2 is 2-hydroxybenzylideneamino and R 8 is an unsubstituted or substituted alkyl, aryl hydrocarbon or ring carbon containing heterocyclic group.
Claim 48
Dependent Claim
53 words
The process according to claim 46, wherein R 8 is n-propyl, carboxymethyl, ethoxycarbonylmethyl, phenyl, 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-ethyl-1,2,3,4-tetrazolyl), 5-(1-sulfomethyl-1,2,3,4-tetrazolyl), 5-(1-carboxymethyl-1,2,3,4-tetrazolyl), 5-[2-(2-carbamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-sulfamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-diethylaminoethyl)-1,2,3,4-tetrazolyl], 5-(1-methoxycarbonylmethyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-(1-phenyl-1,2,3,4-tetrazolyl), 5-(1-vinyl-1,2,3,4-tetrazolyl), 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(5-ethyl-1,3,4-thiadiazolyl), 2-(5-amino-1,3,4-thiadiazolyl), 2-(5-phenyl-1,3,4-thiadiazolyl), 5-(3-methyl-1,2,4-thiadiazolyl), 2-(5-carboxymethyl-1,3,4-thiadiazolyl, 5-(1,2,3-triazolyl), 2-(1-methyl-1,3,4-triazolyl), 2-(5-methyl-1,3,4-triazolyl), 2-(1,5-dimethyl-1,3,4-triazolyl), 4-(5-ethoxycarbonyl-1,2,3-triazolyl), 4-(5-carboxyl-1,2,3-triazolyl), 2-(5-ethoxycarbonylmethyl-1,3,4-triazolyl), benzoxazolyl, 2-(benzimidazolyl), 2-(5-methyl-1,3,4-oxadiazolyl), 2-(5-methyl-1,3-thiazolyl), 2-(5-methyl-1,3-oxazolyl), 2-(1,3-thiazolyl), 5-(1,2,3,4-thiatriazolyl) or 2-(imidazolyl).
Claim 49
Dependent Claim
22 words
The process according to claim 47, wherein R 8 is 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(1-methyl-1,3,4-triazolyl), 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-vinyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], or 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl].
Claim 50
Dependent Claim
23 words
The process according to claim 48, wherein the objective compound is a compound represented by the formula (I) set forth in claim 1.
Claim 51
Dependent Claim
33 words
The process according to claim 49, wherein a compound represented by the formula (II) set forth in claim 1 wherein >Y is >S and X is acetoxy is used as the starting compound.
Claim 52
Dependent Claim
36 words
The process according to claim 1, wherein R 1 is a hydrogen atom, R 2 is a 3, 5-di-tert.-butyl-4-hydroxy-benzylideneamino group and R 8 is unsubstituted or substituted alkyl, aryl hydrocarbon or ring carbon containing heterocyclic group.
Claim 53
Dependent Claim
53 words
The process according to claim 51, wherein R 8 is n-propyl, carboxymethyl, ethoxycarbonylmethyl, phenyl, 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-ethyl-1,2,3,4-tetrazolyl), 5-(1-sulfomethyl-1,2,3,4-tetrazolyl), 5-(1-carboxymethyl-1,2,3,4-tetrazolyl), 5-[2-(2-carbamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-sulfamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-diethylaminoethyl)-1,2,3,4-tetrazolyl], 5-(1-methoxycarbonylmethyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-phenyl-1,2,3,4-tetrazolyl), 5-(1-vinyl-1,2,3,4-tetrazolyl), 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(5-ethyl-1,3,4-thiadiazolyl), 2-(5-amino-1,3,4-thiadiazolyl), 2-(5-phenyl-1,3,4-thiadiazolyl), 5-(3-methyl-1,2,4-thiadiazolyl), 2-(5-carboxymethyl-1,3,4-thiadiazolyl), 5-(1,2,3-triazolyl), 2-(1-methyl-1,3,4-triazolyl), 2-(5-methyl-1,3,4-triazolyl), 2-(1,5-dimethyl-1,3,4-triazolyl), 4-(5-ethoxycarbonyl-1,2,3-triazolyl), 4-(5-carboxyl-1,2,3-triazolyl), 2-(5-ethoxycarbonylmethyl-1,3,4-triazolyl), benzoxazolyl, 2-(benzimidazolyl), 2-(5-methyl-1,3,4-oxadiazolyl), 2-(5-methyl-1,3-thiazolyl), 2-(5-methyl-1,3-oxazolyl), 2-(1,3-thiazolyl), 5-(1,2,3,4-thiatriazolyl) or 2-(imidazolyl).
Claim 54
Dependent Claim
22 words
The process according to claim 52, wherein R 8 is 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(1-methyl-1,3,4-triazolyl), 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-vinyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl] or 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl].
Claim 55
Dependent Claim
23 words
The process according to claim 53, wherein the objective compound is a compound represented by the formula (I) set forth in claim 1.
Claim 56
Dependent Claim
33 words
The process according to claim 54, wherein a compound represented by the formula (II) set forth in claim 1 wherein >Y is >S and X is acetoxy is used as the starting compound.
Claim 57
Dependent Claim
28 words
The process according to claim 2, wherein R 1 is a C 1-4 alkyloxy group and R 8 is an unsubstituted or substituted ring carbon containing heterocyclic group.
Claim 58
Dependent Claim
56 words
The process according to claim 56, wherein R 1 is a methoxy group and R 8 is 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-ethyl-1,2,3,4-tetrazolyl), 5-(1-sulfomethyl-1,2,3,4-tetrazolyl), 5-(1-carboxymethyl-1,2,3,4-tetrazolyl), 5-[2-(2-carbamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-sulfamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-diethylaminoethyl)-1,2,3,4-tetrazolyl], 5-(1-methoxycarbonylmethyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-(1-phenyl-1,2,3,4-tetrazolyl), 5-(1-vinyl-1,2,3,4-tetrazolyl), 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(5-ethyl-1,3,4-thiadiazolyl), 2-(5-amino-1,3,4-thiadiazolyl), 2-(5-phenyl-1,3,4-thiadiazolyl), 5-(3-methyl-1,2,4-thiadiazolyl), 2-(5-carboxymethyl-1,3,4-thiadiazolyl), 5-(1,2,3-triazolyl), 2-(1-methyl-1,3,4-triazolyl), 2-(5-methyl-1,3,4-triazolyl), 2-(1,5-dimethyl-1,3,4-triazolyl), 4-(5-ethoxycarbonyl-1,2,3-triazolyl), 4-(5-carboxyl-1,2,3-triazolyl), 2-(5-ethoxycarbonylmethyl-1,3,4-triazolyl), benzoxazolyl, 2-(benzimidazolyl), 2-(5-methyl-1,3,4-oxadiazolyl), 2-(5-methyl-1,3-thiazolyl), 2-(5-methyl-1,3-oxazolyl), 2-(1,3-thiazolyl), 5-(1,2,3,4-thiatriazolyl) or 2-(imidazolyl).
Claim 59
Dependent Claim
22 words
The process according to claim 57, wherein R 8 is 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(1-methyl-1,3,4-triazolyl), 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-vinyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl] or 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl].
Claim 60
Dependent Claim
23 words
The process according to claim 58, wherein the objective compound is a compound represented by the formula (I) set forth in claim 1.
Claim 61
Dependent Claim
33 words
The process according to claim 59, wherein a compound represented by the formula (II) set forth in claim 1 wherein >Y is >S and X is acetoxy is used as the starting compound.
Claim 62
Dependent Claim
20 words
The process according to claim 2, wherein R 1 is a hydrogen atom, >Y is >S→O and X is acetoxy.
Claim 63
Dependent Claim
20 words
The process according to claim 2, wherein R 1 is a hydrogen atom, >Y is >S and X is acetoxy.
Claim 64
Dependent Claim
28 words
The process according to claim 45, wherein a salt of the compound represented by the formula (II) set forth in claim 1 is used as the starting compound.
Claim 65
Dependent Claim
26 words
The process according to claim 42, wherein the objective compound is an ester of the compound represented by the formula (I) set forth in claim 1.
Claim 66
Dependent Claim
26 words
The process according to claim 42, wherein the objective compound is a salt of the compound represented by the formula (I) set forth in claim 1.
Claim 67
Dependent Claim
40 words
The process according to claim 44, wherein a compound represented by the formula (II) set forth in claim 1 wherein >Y is >S, and X is carboxylic acyloxy having 1 to 8 carbon atoms is used as the starting compound.
Claim 68
Dependent Claim
20 words
The process according to claim 45, wherein the organic solvent is a nitrile, ether, nitroalkane, organic carboxylic acid or sulfolane.
Claim 69
Dependent Claim
18 words
The process according to claim 45, wherein the reaction is effected in the presence of a dehydrating agent.
Claim 70
Dependent Claim
17 words
The process according to claim 45, wherein the reaction is effected in the presence of boron trilfuoride.
Claim 71
Dependent Claim
35 words
The process according to claim 45, wherein the boron trifluoride complex compound is a dialkyl ether complex, an amine complex, an aliphatic acid complex, a nitrile complex, a carboxylic ester complex or a phenol complex.
Claim 72
Dependent Claim
25 words
The process according to claim 45, wherein the boron trifluoride complex compound is a dialkyl ether complex, an aliphatic acid complex or a nitrile complex.
Claim 73
Dependent Claim
17 words
The process according to claim 67, wherein the reaction is effected in the presence of boron trifluoride.
Claim 74
Dependent Claim
18 words
The process according to claim 72, wherein the reaction is effected in the presence of a dehydrating agent.
Claim 75
Dependent Claim
28 words
The process according to claim 72, wherein a salt of the compound represented by the formula (II) set forth in claim 1 is used as the starting compound.
Claim 76
Dependent Claim
26 words
The process according to claim 72, wherein the objective compound is an ester of the compound represented by the formula (I) set forth in claim 1.
Claim 77
Dependent Claim
26 words
The process according to claim 72, wherein the objective compound is a salt of the compound represented by the formula (I) set forth in claim 1.
Claim 78
Dependent Claim
20 words
The process according to claim 1, wherein the organic solvent is in the form of a complex with boron trifluoride.
Claim 79
Dependent Claim
11 words
The process according to claim 45, wherein R 8 is 5-(1-methyl-1,2,3,4-tetrazolyl).
Claim 80
Dependent Claim
11 words
The process according to claim 50, wherein R 8 is 5-(1-methyl-1,2,3,4-tetrazolyl).
Claim 81
Dependent Claim
11 words
The process according to claim 55, wherein R 8 is 5-(1-methyl-1,2,3,4-tetrazolyl).
Claim 82
Dependent Claim
11 words
The process according to claim 65, wherein R 8 is 5-(1-methyl-1,2,3,4-tetrazolyl).
Claim 83
Dependent Claim
11 words
The process according to claim 45, wherein R 8 is 2-(5-methyl-1,3,4-thiadiazolyl).
Claim 84
Dependent Claim
40 words
The process according to claim 72, wherein the boron trifluoride or boron trifluoride complex compound is used in an amount of 2 to 7 moles per mole of the compound represented by the formula (II) set forth in claim 1.
Claim 85
Dependent Claim
34 words
The process according to claim 72, wherein the amount of the thiol compound represented by the general formula (III) is 1 to 1.5 moles per mole of the compound represented by the formula (II).
Claim 86
Dependent Claim
26 words
The process according to claim 45, wherein the organic solvent is a complex of a nitrile, an ether or an aliphatic acid with a boron trifluoride.
Claim 87
Dependent Claim
26 words
The process according to claim 82, wherein the organic solvent is a complex of a nitrile, an ether or an aliphatic acid with a boron trifluoride.
Claim 88
Dependent Claim
50 words
The process according to claim 36, wherein R 8 is a 5-(1,2,3,4-tetrazolyl), 5-(1-methyl-1,2,3,4-tetrazolyl), 5-(1-ethyl-1,2,3,4-tetrazolyl), 5-(1-sulfomethyl-1,2,3,4-tetrazolyl), 5-(1-carboxylmethyl-1,2,3,4-tetrazolyl), 5-[2-(2-carbamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-sulfamoylethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[2-(2-N,N-dimethylaminoethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-N,N-diethylaminoethyl)-1,2,3,4-tetrazolyl], 5-(1-methoxycarbonylmethyl-1,2,3,4-tetrazolyl), 5-(1-carbamoylmethyl-1,2,3,4-tetrazolyl), 5-[1-(2-aminoethyl)-1,2,3,4-tetrazolyl], 5-[1-(2-hydroxyethyl)-1,2,3,4-tetrazolyl], 5-(1-phenyl-1,2,3,4-tetrazolyl), 5-(1-vinyl-1,2,3,4-tetrazolyl), 2-(1,3,4-thiadiazolyl), 2-(5-methyl-1,3,4-thiadiazolyl), 2-(5-ethyl-1,3,4-thiadiazolyl), 2-(5-amino-1,3,4-thiadiazolyl), 2-(5-phenyl-1,3,4-thiadiazolyl), 5-(3-methyl-1,2,4-thiadiazolyl), 2-(5-carboxymethyl-1,3,4-thiadiazolyl), 5-(1,2,3-triazolyl), 2-(1-methyl-1,3,4-triazolyl), 2-(5-methyl-1,3,4-triazolyl), 2-(1,5-dimethyl-1,3,4-triazolyl), 4-(5-ethoxycarbonyl-1,2,3-triazolyl), 4-(5-carboxyl-1,2,3-triazolyl), 2-(5-ethoxycarbonyl-1,3,4-triazolyl), benzoxazolyl, 2-(benzimidazolyl), 2-(5-methyl-1,3,4-oxadiazolyl), 2-(5-methyl-1,3-thiazolyl), 2-(5-methyl-1,3-oxazolyl), 2-(1,3-thiazolyl), 5-(1,2,3,4-thiatriazolyl) or 2-(imidazolyl).
Claim 89
Dependent Claim
19 words
The process of claim 1 wherein the complex compound of boron trifluoride is a coordination compound of boron trifluoride.
References Cited (Backward Citations)
DE1795484U
Cited
BE650445A
Cited
BE650444A
Cited
US3261832A
Cited
US3516997A
Cited
DE2065621A1
Cited
US3833572A
Cited
US3872115A
Cited
GB1400804A
Cited
US3840531A
Cited
DE2332045A1
Cited
US4014874A
Cited
DE2530622A1
Cited
DE2537974A1
Cited
US4144391A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-03-01 | 1985-08-31 | 1986-03-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-03-01 | 1989-08-31 | 1990-03-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-03-01 | 1993-08-31 | 1994-03-02 | $7700.00 | Window Closed / Lapsed |