EP1019381A1 - Procede d'elaboration de composes n, n'-diazole - Google Patents

Procede d'elaboration de composes n, n'-diazole

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Publication number
EP1019381A1
EP1019381A1 EP98901791A EP98901791A EP1019381A1 EP 1019381 A1 EP1019381 A1 EP 1019381A1 EP 98901791 A EP98901791 A EP 98901791A EP 98901791 A EP98901791 A EP 98901791A EP 1019381 A1 EP1019381 A1 EP 1019381A1
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EP
European Patent Office
Prior art keywords
unsubstituted
compound
azole
organic base
molar ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98901791A
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German (de)
English (en)
Inventor
Robert H. Tang
Suresh B. Damle
Seetha L. Eswarakrishnan
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PPG Industries Inc
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PPG Industries Inc
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Filing date
Publication date
Application filed by PPG Industries Inc filed Critical PPG Industries Inc
Publication of EP1019381A1 publication Critical patent/EP1019381A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to a method of producing N,N'-diazole compounds selected from the group consisting of N,N' -carbonyldiazole, N,N-carbonothioicdiazole, and N,N'- thionyldiazole compounds. More particularly, the present invention relates to a method of preparing such N,N'-diazole compounds by reacting a 1-unsubstituted IH-azole compound with a dihalide compound, e.g., phosgene, in the presence of an inert solvent and an organic base, e.g., a tertiary amine.
  • a dihalide compound e.g., phosgene
  • Che molar ratio of the 1-unsubstituted IH-azole to the dihalide compound need not exceed 2:1.
  • N,N'-diazole compounds prepared in accordance with the present invention have been found to have acceptable color.
  • N,N'-diazole compounds such as N,N' -carbonyldiazole, N,N' -carbonothioicdiazole and N,N' -thionyldiazole compounds, are useful as reagents for introducing carbonyl, carbonothioic, thionyl or azole groups into other compounds without formation of a hydrohalide acid co-product. They are more convenient to handle and easier to measure than dihalide compounds, such as phosgene. They are useful in reactions involving dehydration, ester formation and isocyanate formation, and as enzyme and protein binding agents. Further, these diazole compounds are also useful as intermediates for synthesizing medicines and agricultural chemicals. For example, U.S. Patent No. 4,237,709 describes the use of N,N'- carbonyldiazole compounds in the preparation of antibiotics and peptides .
  • N,N' -carbonyldiazole, N,N'- carbonothioicdiazole and N,N ! -thionyldiazole compounds can each typically be produced by a method involving the reaction of a 1-unsubstituted IH-azole compound and a dihalide compound such as, respectively phosgene, carbonothioic dichloride and thionyl chloride, each in a molar ratio of 4:1. See for example, . Forest, Newer Methods of Preparative Organic
  • N,N' -carbonyldiazole compounds and more specifically N,N' -carbonyldiimidazole
  • such a prior art method may be represented by the following general scheme I.
  • the method represented by general scheme I can be expensive in that: (a) only half of the 1-unsubstituted 1H- azole compound present at the beginning of the reaction is used to form the desired N,N' -carbonyldiazole; and (b) the separation of the precipitated N,N' -carbonyldiazole compound from the precipitated 1-unsubstituted IH-azole hydrohalide salt is typically a multi-step process requiring additional time and materials.
  • United States Patents 3,991,071, 4,080,462 and 4,154,945 disclose a method of preparing carbonylbisimidazole which includes reacting, in an inert solvent, phosgene and IH- imidazole in the presence of an acid-binding agent.
  • the acid- binding agent is described as being a tertiary amine such as triethylamine, pyridine or excess imidazole .
  • Preferred levels of the acid-binding agent and molar ratios of the acid-binding agent to the IH-imidazole are not disclosed in United States Patents 3,991,071, 4,080,462 or 4,154,945.
  • United States Patent 5,552,554 discloses a process of preparing a carbonylating agent, such as N,N'- carbonyldiimidazole or N,N' -carbonyldi (1, 2, 4-triazole) , in- situ by reacting, in the presence of a hydroxyl functional ester and an inert solvent, phosgene and one of IH-imidazole or lH-l,2,4-triazole and an organic base selected from the group consisting of trialkylamine, pyridine, picoline or other substituted pyridine.
  • a carbonylating agent such as N,N'- carbonyldiimidazole or N,N' -carbonyldi (1, 2, 4-triazole
  • Preferred molar ratios of the organic base to the IH-imidazole or 1H-1, 2 , 4, -triazole are not disclosed in United States Patent 5,552,554.
  • Examples 2, 5 and 11 in columns 7, 8 and 10 respectively of United States Patent 5,552,554 describe in-situ preparations of N,N'- diazoles wherein the molar ratio of the organic base to 1H- azole compound is in each case greater than 1:1 when the molar ratio of 1-unsubstituted IH-azole compound to phosgene is less than 2:1.
  • discolored, e.g., brown, N,N'- diazole compounds can result from the reaction, in an inert solvent, of a 1-unsubstituted IH-azole compound, e.g., IH- imidazole, and an excess of a dihalide compound, e.g., phosgene, in the presence of an excess of an organic base such as a tertiary amine.
  • a 1-unsubstituted IH-azole compound e.g., IH- imidazole
  • a dihalide compound e.g., phosgene
  • N,N'- diazole compounds having a minimum of discoloration such as N,N' -carbonyldiazole, N,N' -carbonothioicdiazole and N,N'- thionyldiazole compounds, that is more efficient in terms of the utilization of starting materials, and the process of isolating the desired product.
  • N,N' -diazole compounds such as N,N' -carbonyldiazole compounds, can be produced by reacting a 1-unsubstituted IH-azole compound and a dihalide compound, e.g., phosgene, in a molar ratio that need not exceed 2:1.
  • phosgene e.g., phosgene
  • N,N' -diazole compound selected from the group consisting of N,N' -carbonyldiazole, N,N'- carbonothioicdiazole, and N,N' -thionyldiazole compounds, comprising reacting in an inert solvent and in the presence of an organic base, a 1-unsubstituted IH-azole compound represented by the following general formula I:
  • X , X and X are independently CR or nitrogen provided that at least one of X 1 , X and X is nitrogen, R 1 and R 2 are independently hydrogen, halogen such as chlorine and bromine, C x - C e alkyl, phenyl, substituted phenyl, or when X 3 is CR 1 together form a fused ring having 4 to 6 carbon atoms inclusive of the two carbon atoms in the 1-unsubstituted IH- azole ring through which R and R are connected; with a dihalide compound selected from a member of the group consisting of:
  • the molar ratio of the 1-unsubstituted IH-azole compound to the dihalide compound can vary from 1.7:1 to 2.3:1, preferably from 1.8:1 to 2:1, and more preferably from 1.9:1 to 2:1.
  • the organic base is soluble in the inert solvent, has a basicity greater than that of the 1-unsubstituted IH-azole compound, and forms a hydrohalide salt that is soluble in the inert solvent.
  • the molar ratio of the organic base to the 1- unsubstituted IH-azole compound is 1:1 when the molar ratio of the 1-unsubstituted IH-azole compound to the dihalide compound is less than 2:1.
  • the 1-unsubstituted IH-azole compounds useful in the method of the present invention contain only one secondary amino group which is located in the 1-position of the azole ring, as described in general formula I above.
  • substituted phenyl is meant C - C 6 alkyl substituted phenyl, halogen, e.g., chlorine and bromine, substituted phenyl or C ⁇ - C 6 alkyl and halogen substituted phenyl .
  • the substituents R 1 and R 2 are chosen such that they do not preclude the desired reaction at the 1-position.
  • 1-unsubstituted IH-azole compounds described with reference to general formula I, wherein X 2 is nitrogen, and X 1 and X 3 are each CR 1 , are commonly referred to as 1- unsubstituted lH-imidazoles, or lH-imidazoles .
  • Examples of lH-imidazoles useful in the method of the present invention include, but are not limited to: IH-imidazole; 1H-4- methylimidazole; lH-5-methylimidazole; lH-4-ethyl-5- methylimidazole; 1H-2, 4-dimethylimidazole; 1H-2- phenylimidazole; lH-4-phenylimidazole; 1H-5-phenylimidazole; 1H-2 , 4, 5-triphenylimidazole; lH-2-methyl-4 , 5- diphenylimidazole; lH-4-bromoimidazole; lH-5-bromoimidazole; 1H-4-bromo-5-methylimidazole; lH-4-methyl-5-bromoimidazole; lH-4-bromo-5-phenylimidazole; lH-4-phenyl-5-bromoimidazole; 1H-2 , 4-dibro
  • 1-unsubstituted IH-azole compounds described with reference to general formula I, wherein X 1 is nitrogen, and X 2 and X 3 are CR 1 are commonly referred to as 1-unsubstituted 1H- pyrazoles or lH-pyrazoles .
  • Examples of lH-pyrazoles useful in the method of the present invention include, but are not limited to: lH-pyrazole; 3 , 5-dimethyl-lH-pyrozole; and 1H- indazole.
  • 1-unsubstituted IH-azole compounds described with reference to general formula I, wherein X 1 and X 2 are both nitrogen and X 3 is CR 1 are commonly referred to as 1- unsubstituted 1H-1, 2, 3-triazoles, or 1H-1, 2 , 3-triazoles .
  • Examples of 1H-1, 2 , 3-triazoles useful in the method of the present invention include, but are not limited to, 1H-1,2,3- triazole and 1H-1, 2 , 3-benzotriazole.
  • 1-unsubstituted IH-azole compounds described with reference to general formula I, wherein X 2 and X 3 are both nitrogen, and X is CR are commonly referred to as 1- unsubstituted 1H-1, 2, 4-triazoles, or 1H-1, 2 , 4-triazoles .
  • Examples of 1H-1, 2 , 4-triazoles useful in the method of the present invention include, but are not limited to, 1H-1,2,4- triazole and lH-5-methyl-l, 2 , 4-triazole .
  • Azole compounds described with reference to general formula I, wherein X , X and X are each nitrogen are commonly referred to as tetrazoles .
  • Such tetrazoles can be represented by two tautomeric forms, IH-tetrazole and 2H-tetrazole. Conversion between the two tautomeric forms is thought to occur through a proton shift.
  • general formula I is representative of tetrazoles having the 2H-tetrazole tautomeric form, it is also meant to be representative of tetrazoles having the more prevalent IH-tetrazole tautomeric form.
  • IH-azole compounds useful in the method of the present invention include: IH-imidazole; 1H- benzimidazole; lH-pyrazole; lH-indazole; 1H-1, 2 , 3-triazole;
  • a particularly preferred 1-unsubstituted IH-azole compound is IH-imidazole.
  • a single l-unsubstituted IH-azole compound or a mixture of such compounds may be used as desired. The use of a single 1- unsubstituted IH-azole compound is preferred.
  • a l-unsubstituted IH-azole compound is reacted with a dihalide compound, as described above, to form N,N' -carbonyldiazole, N,N- carbonothioicdiazole, or N,N' -thionyldiazole compounds.
  • the molar ratio of the l-unsubstituted IH-azole compound to the dihalide compound may range from 1.7:1 to 2.3:1, preferably from 1.8:1 to 2:1 and more preferably from 1.9:1 to 2:1.
  • the molar ratio of the 1- unsubstituted IH-azole compound to the dihalide compound is preferably 2:1.
  • an excess of the dihalide compound e.g., phosgene, may be used.
  • an excess of the dihalide compound e.g., phosgene, which can be as high as 20% molar excess, is often present because of the difficulty in accurately measuring such dihalide compounds, which are typically in the gas phase under the reaction conditions employed.
  • the method of the present invention is conducted in the presence of an inert solvent as the reaction medium, which is preferably a solvent for the reactants.
  • inert it is meant a solvent which will not interfere or otherwise preclude the reaction between the l-unsubstituted IH-azole and dihalide compound.
  • Classes of inert solvents useful in the practice of the present invention include, but are not limited to, alkanes, aromatic solvents, halogenated solvents, ethers, dioxanes, esters, amides and ureas.
  • Halogenated and aromatic solvents are the preferred classes of inert solvents .
  • inert solvents which may be used include: alkanes such as, hexane, heptane and octane; aromatic solvents, such as toluene, benzene, cumene, mesitylene, propylbenzene, anisole and xylene; halogenated solvents, such as methylene chloride, chlorobenzene, and 1, 2-dichloroethane,- ethers such as, tetrahydrofuran, diethyl ether and 1,2- dimethoxyethane ; dioxanes such as 1, 4-dioxane; esters such as, methyl acetate and ethyl acetate; amides such as, N,N- dimethylformamide and N-methyl-1, 2-pyrrolidine; and ureas such as 1, 3-dimethyl-2-imidaxolidinone.
  • alkanes such as, hexane, heptane and octane
  • Preferred inert solvents are the organic solvents methylene chloride and toluene.
  • a particularly preferred inert solvent is toluene.
  • the inert solvent is present in an amount sufficient to solubilize the reactants .
  • the method of the present invention is conducted also in the presence of an organic base which has a basicity greater than that of the l-unsubstituted IH-azole compound.
  • the reaction between the l-unsubstituted IH-azole compound and the dihalide compound results in the formation of a hydrohalide acid co-product, e.g., hydrochloric acid in the case of phosgene.
  • a basicity greater than that of the 1- unsubstituted IH-azole compound is meant that the formation of the hydrohalide salt of the organic base is at least thermodynamically favored, and preferably also kinetically favored, over the formation of the l-unsubstituted IH-azole hydrohalide salt.
  • Hydrohalide salt formation which occurs predominantly between the organic base and the hydrohalide acid, allows the l-unsubstituted IH-azole compound to be free to react with the dihalide compound.
  • Any organic base, or mixture of organic bases which: has a basicity greater than that of the l-unsubstituted IH- azole compound; will not form a covalent bond with the dihalide compound; and together with its hydrohalide salt is soluble in the inert solvent of the reaction mixture, may be used in the practice of the present invention.
  • the molar ratio of the organic base to the l-unsubstituted IH-azole compound is 1:1, provided the molar ratio of the l-unsubstituted IH- azole compound to the dihalide compound is less than 2:1.
  • the molar ratio of the l-unsubstituted IH-azole compound to the dihalide compound is less than 2:1, it is necessary that the ratio of the organic base to the l-unsubstituted IH- azole compound not exceed 1:1, so that formation of a discolored N,N' -diazole compound is minimized.
  • the presence of the organic base in a molar ratio of 1:1 with the l-unsubstituted IH-azole compound also allows for the use of only that amount of l-unsubstituted IH-azole compound that is desired to be incorporated through covalent bond formation into the N,N' -diazole compound product.
  • the ratio of IH-imidazole to the dihalide compound, e.g., phosgene need not exceed 2:1.
  • the molar ratio of the organic base to the l-unsubstituted IH-azole compound may be 1:1 or greater. Since the method of the present invention does not require the presence of an excess of the organic base, it is preferable under these circumstances that the molar ratio of the organic base to the l-unsubstituted IH- azole compound be 1:1.
  • the molar ratio of the organic base to the l-unsubstituted IH-azole compound may be 1:1 or greater, or the molar ratio of the organic base to the dihalide compound may be 2:1 or greater. Since the method of the present invention does not require the presence of an excess of the organic base, it is preferable under these circumstances that the molar ratio of the organic base to the dihalide compound be 2:1.
  • the organic base and its hydrohalide salt are both soluble in the inert solvent of the reaction mixture. This allows for the facile separation of a N,N' -diazole compound that is substantially free of the hydrohalide salt of the organic base.
  • N,N' -carbonyldiimidazole produced according to the method of the present invention may be isolated from the reaction mixture as a precipitate which is substantially free of the hydrohalide salt of the organic base.
  • the hydrohalide salt of the organic base may be present in the precipitated N,N' -diazole compound, it is understood by those skilled in the art that the purity of the N,N' -diazole product may be further increased by washing with additional solvent followed by drying.
  • the organic base is preferably a tertiary amine.
  • tertiary amines useful in the method of the present invention include: tri (aryl) amines, e.g., wherein each aryl group contains from 6 to 9 carbon atoms, such as triphenylamine and tribenzylamine; tri (alkyl) amines, such as, trimethylamine, triethylamine, N,N-dimethylethylamine, tri (n-propyl) amine, tri (isopropyl) amine, tri (n-butyl) amine, tripentylamine, trihexylamine, trioctylamine, tridecylamine and tridodecylamine.
  • tertiary amines include 1- methylpyrrolidine, 1-methylpyrrole and 1-methylpiperidine.
  • the tri (alkyl) amines wherein each alkyl group contains from 1 to 12, e.g., 1 to 6, carbon atoms are preferred, with tri (n- butyl) amine being particularly preferred.
  • the l-unsubstituted lH-diazole and dihalide compounds may be charged to the reactor in any order. They may be introduced concurrently or sequentially. The addition may be continuous or intermittent. In a preferred embodiment of the present invention, an appropriate amount of dihalide compound is slowly introduced into a suitable reaction vessel containing appropriate amounts of inert solvent, 1- unsubstituted lH-diazole compound and tertiary amine.
  • the temperature at which the reaction of the method of the present invention is conducted may vary considerably, but ordinarily is at a temperature at which the solvent is liquid, and is in the range of from 15°C to 150°C. A temperature of from 50 °C to 80 °C is preferred, particularly when the inert solvent used is toluene.
  • the pressure at which the reaction of the method of the present invention is conducted is also subject to wide variation. Atmospheric and slightly superatmospheric pressures are generally employed since the reaction is in the liquid phase, although greater or lesser pressures may be used. Preferably the pressure at which the reaction is conducted is atmospheric pressure.
  • EXAMPLE 1 This example describes the preparation of N,N'- carbonyldiimidazole by a method approximating that represented in General Scheme I, using the following enumerated ingredients .
  • Charge 1 was added to a 1 liter four-necked flask fitted with a motor-driven stir blade, a temperature probe and heating mantle (both of which were connected to a temperature feed-back control device) , a phosgene and nitrogen inlet tube, the outlet of which was set above the liquid surface within the flask, and a cold condenser vented to a caustic scrubber.
  • the contents of the flask were then heated to a temperature of about 65°C under a nitrogen purge. With the nitrogen purge turned off, Charge 2 was fed into the flask over a period of 20 to 30 minutes, during which time an exotherm peak of 82°C was observed.
  • the contents of the flask were allowed to cool and degas under a nitrogen purge.
  • the contents of the flask were heated to 80 °C and filtered under nitrogen through a heated 70 to 100 micron glass fritted filter.
  • the collected solids were washed two times each with 173 grams of toluene heated to a temperature of 80°C.
  • the filtrates were collected into a single vessel and allowed to slowly cool to room temperature with stirring under a nitrogen purge, during which time white crystals began precipitating from the filtrate.
  • the precipitate was collected under nitrogen using a 70 to 100 micron glass fritted filter.
  • This example describes the preparation of N,N'- carbonyldiimidazole using tri (n-butyl) amine as the organic base, wherein the molar ratio of tri (n-butyl) amine to IH- imidazole is 1.1:1.0 while the molar ratio of IH-imidazole to phosgene is less than 2.0:1.0.
  • Charge 1 was added to a 1 liter four-necked flask fitted with a motor-driven stir blade, a temperature probe and heating mantle (both of which were connected to a temperature feed-back control device) , a phosgene and nitrogen inlet tube, the outlet of which was set above the liquid surface within the flask, and a cold condenser vented to a caustic scrubber.
  • the contents of the flask were heated to a temperature of about 65°C to 70°C under a nitrogen purge. With the nitrogen purge turned off, Charge 2 was fed into the flask over a period of about 20 minutes, while maintaining the contents of the flask at a temperature of 70°C to 75°C.
  • N,N' -carbonyldiimidazole was prepared in accordance with the method of the present invention using the following enumerated ingredients.
  • Charge 1 was added to a 500 ml four-necked flask fitted with a motor driven stir blade, a temperature probe and heating mantle (both of which were connected to a temperature feed-back control device) , a phosgene and nitrogen inlet tube the outlet of which was set above the liquid surface within the flask, and a cold condenser vented to a caustic scrubber.
  • the contents of the flask were heated to a temperature of about 65°C to 70°C under a nitrogen purge. With the nitrogen purge turned off, Charge 2 was fed into the flask over a period of from 20 to 30 minutes, while maintaining the contents of the flask at a temperature of 70°C to 75°C.
  • the % Yield was determined using the following equation, lOOx (actual grams of precipitate collected / theoretical grams of product) .
  • Table 1 shows that the method of the present invention is more efficient than that of the prior art method represented in General Scheme I, in terms of producing N,N'- carbonyldiimidazole.
  • the method of the present invention as represented by Example 3 produces a higher yield of product while using less raw materials, i.e. 1H- imidazole.
  • the % Weight Ionic Chloride was determined by dissolving a known amount of the isolated precipitated product in water acidified with nitric acid, followed by potentiometric titration of the chloride ion (anion) with AgN0 3 using a silver billet electrode to detect the end point. This method is not specific as to the source of the chloride ion.
  • the data of Table 2 shows that the method of the present invention, as represented by Example 3, results in the production of N,N' -carbonyldiimidazole having a white color which is essentially equivalent to that of the prior art method represented by Example 1.
  • the data of Table 2 also shows the criticality of maintaining the molar ratio of the tertiary amine to IH-imidazole at 1:1 when the molar ratio of IH-imidazole to phosgene is less than 2:1, in comparing Examples 2 and 3.

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Abstract

Procédé d'élaboration de composés N, N'-diazole, par exemple N, N'-carbonyldiimidazole, consistant à établir la réaction dans un solvant inerte, par exemple toluène, d'un composé 1H-azole 1-non substitué, par exemple 1H-imidazole, et d'un composé dihaloïde, par exemple phosgène, en présence d'une base organique, par exemple amine tertiaire du type tri(n-butyl)amine. Le rapport molaire entre le composé 1H-azole non substitué en 1 et le composé dihaloïde peut aller de 1,7: 1 à 2,3: 1. Le rapport molaire entre la base organique et le composé 1H-azole non substitué en 1 est 1: 1 lorsque le rapport molaire entre le composé 1H-azole non substitué en 1 et le composé dihaloïde est inférieur à 2: 1. La base organique a une basicité supérieure à celle du composé 1H-azole non substitué en 1, et elle est soluble dans le solvant inerte avec son sel d'hydrohaloïde.
EP98901791A 1997-01-17 1998-01-09 Procede d'elaboration de composes n, n'-diazole Withdrawn EP1019381A1 (fr)

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US785626 1991-10-31
US78562697A 1997-01-17 1997-01-17
PCT/US1998/000592 WO1998031672A1 (fr) 1997-01-17 1998-01-09 Procede d'elaboration de composes n, n'-diazole

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WO1998031672A1 (fr) 1998-07-23
CN1248247A (zh) 2000-03-22
CA2278179A1 (fr) 1998-07-23

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