CA2005330A1 - Explosion-proof 1-dimethylamino-3-dimethylimino-2-aryl-1-propene salts, processes for their preparation and their use - Google Patents
Explosion-proof 1-dimethylamino-3-dimethylimino-2-aryl-1-propene salts, processes for their preparation and their useInfo
- Publication number
- CA2005330A1 CA2005330A1 CA002005330A CA2005330A CA2005330A1 CA 2005330 A1 CA2005330 A1 CA 2005330A1 CA 002005330 A CA002005330 A CA 002005330A CA 2005330 A CA2005330 A CA 2005330A CA 2005330 A1 CA2005330 A1 CA 2005330A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- trimethine
- salts
- water
- naphthalene
- 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.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/30—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups quaternised
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
- ? -Abstract:
Preparation of explosion-proof trimethine salts of slight solubility in water which have the formula I
(I) in which R is aryl or heteroaryl which is unsubstituted or mono-or polysubstituted and X is the anion equivalent of a non-oxidizing acid radical which is inert towards the trimethine cation and can form trimethine salts of slight solubility in water, by formylation of compounds of the formula II
R-CH2-COOH (II) in which R is as defined in formula I under the condi-tions of the Vilsmeier-Haack reaction, followed by hydrolysis of the formylation product in aqueous medium with the formation of water-soluble primary trimethine salts and reaction of the water-soluble primary tri-methine salts in the aqueous reaction mixture with acids of the formula III
(H)nX (III) in which X is as defined in formula I and n is a number from 1 to 3, or water-soluble salts thereof in at least stoichiometric amounts and separating off the resulting trimethine salts of slight solubility in water which have the formula I.
Trimethine salts of the formula I are used as inter-mediates for the synthesis of heterocycles, preferably of pyrimidines and pyridines.
Preparation of explosion-proof trimethine salts of slight solubility in water which have the formula I
(I) in which R is aryl or heteroaryl which is unsubstituted or mono-or polysubstituted and X is the anion equivalent of a non-oxidizing acid radical which is inert towards the trimethine cation and can form trimethine salts of slight solubility in water, by formylation of compounds of the formula II
R-CH2-COOH (II) in which R is as defined in formula I under the condi-tions of the Vilsmeier-Haack reaction, followed by hydrolysis of the formylation product in aqueous medium with the formation of water-soluble primary trimethine salts and reaction of the water-soluble primary tri-methine salts in the aqueous reaction mixture with acids of the formula III
(H)nX (III) in which X is as defined in formula I and n is a number from 1 to 3, or water-soluble salts thereof in at least stoichiometric amounts and separating off the resulting trimethine salts of slight solubility in water which have the formula I.
Trimethine salts of the formula I are used as inter-mediates for the synthesis of heterocycles, preferably of pyrimidines and pyridines.
Description
HOECHST AK~IENGESELLSCHAFT HOE 88/F 362 Dr.JA/PP
.; .
- - Description Explosion-proof 1-dimethylamino-3-dimethylimino-2-aryl-l-propene salts, proces3es for their preparation and their use As is known, 1-dimethylamino-3-dimethylimino-2-aryl-1-propene perchlorates are important intermediates for the synthesis of heterocycles, such as, for example, pyrimi-dines (cf. Zaschke, Z. Chem. 17 (1977) p. 63 and 293;
Arnold, Collect. Czech. Chem. Commun. 38 (1978) 1371;
Zaschke, J. prakt. Chemie 321 (1979) 619) and pyridines (cf. C.A. 109:64513w, (1988)). Preparative methods for this class of compounds, which is also known by the short name trimethine perchlorates, are also known. It is furthermore known that these perchlorates, which are - slightly soluble in water, are explosive to highly explosive products when dry (cf. Chem. Eng. News 52 (1974) No. 31, p. 3), the handling of which in their possible use as intermediates is extremely dangerous.
~heir industrial use is therefore virtually precluded.
Accordingly, the ob~ect of the present invention was to provide trimethine salts which can be handled in an explosion-proof manner, can be prepared without difficul-ties in the purity required, and can otherwise be usedlike the perchlorates, but without risk of explosion, as intermediates, inter alia, for the syntheses of the abovementioned heterocycles.
Surprisingly, it has now been found that, while avoiding the use of perchlorate as anion, explosion-proof trimeth-ine salts of low to slight solubility in water can be obtained by reacting water-soluble trimethine salts in aqueous medium with non-oxidizing acids which can form trimethine salts of low to slight solubility in water and are inert towards the trimethine cation, or with water-soluble salts of these non-oxidizing acids and isolating , : , . . . .
- , ,, .. . ..
,, .:. ,, . , . :
"
~005330 . -- 2 --the trimethine salts of low to slight solubility which precipitate in the aqueous phase, preferably by filtra-tion or by centrifugation, and, if desired, purifying them further by washing and/or, if desired, by reprecipi-tation and, if desired, drying them.
The invention accordingly relates to explosion-proof trimethine salts of low to slight solubility in water which have the formula I
,~CH-N(cH3)2 R^C (+) X( ) (I) CH=N(cH3)2 in which R and X have the following meaningss R is aryl or heteroaryl which are unsubstituted or mono-or polysubstituted by halogen, (C1-C~)-alkyl, (C1-C12)-alkoxy or hydroxyl, in which aryl is preferably phenyl, naphthyl, biphenylyl, anthracenyl or tetra-linyl and heteroaryl is preferably pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, halogen is preferably F, Cl or Br, in particular F or Cl, and the radic~ls (C1-C12)-alkyl and (C1-C12)-alkoxy are unsubstituted or mono- or polysubstituted by halo-gen, in particular F or Cl;
X is the anion equivalent of a non-oxidizing acid radical which is inert towards the trimethine cation and can form trimethine salts of slight solubility in water, preferably from the group p-toluenesulfonate, naphthalene-2-sulfonate, naphthalene-l-sulfonate, naphthalene-1,5-disulfonate, BF4~-), SbF8~-), PF5(-), AlF6~-), in particular PF6(-) and naphthalene-2-sul-fonate.
The invention furthermore relates to a process for the preparation of explosion-proof trimethine ~alts of the abovementioned formula I by formylation of compounds of , . . . . . .
.
, ',: . ' , . : .
.. ..
- 200s~30 the formula II
R-CH2-COOH (II) in which R is as defined in formula I under the condi-tions of the Vilsmeier-Haack reaction, followed by hydrolysis of the formylation product in aqueous medium with the formation of water-soluble primary trimethine salts, which comprises adding mono- or polybasic acids of the formula III
(H)nX (III) in which X is as defined in formula I and n is a number from 1 to 3, preferably 1 or 2, in particular 1, or water-soluble salts thereof in at least stoichiometric amounts to the aqueous reaction mixture containing the ~ater-soluble primary trimethine salts and separating off - 15 the resulting trimethine salts of the formula I, of slight solubility in water, in a preferably fine-crystal-line form.
Preferred acids of the formula III or water-soluble salts thereof are p-toluenesulfonic acid, sodium p-toluene-sulfonate, sodium tetrafluoroborate, sodium hexafluoro-antimonate, sodium hexafluorophosphate, sodium hexa-fluoroaluminate, naphthalene-2-sulfonic acid, sodium naphthalene-2-sulfonate, sodium naphthalene-l-sulfonate, disodium naphthalene-1,5-disulfonate, or mixtures of these salts or scids, in particular with the acids or salts based on them. Hexafluorophosphate and naphthalene-2-sulfonate are particularly preferred.
The trimethine salts of the formula I prepared according to the invention are preferably formed in a fine-crystal-line form and can be easily separated off from the motherliquor, washed with water and, if desired, subsequently dried, after which they are typically obtained in a purity of over 99%. To purify them further, they can, if , ' ' " ., ' ' ...... , ~ . : .
.
,, , . , , . . :
:, , ': ,' , . . .
",' " ' ', ' ' ' ,: , , . . ~ . , , , "" '., ' :
~005330 desired, additionally be recrystallized from suitable solvents, which is however, in general not necessary for their further use as intermediates for the synthesis of heterocycles, since they are already excellent synthetic components even without additional purification. Guiding tests in this direction have also shown that, when the compounds according to the invention of the formula I are used as starting materials for pyrimidine syntheses, the anion of the compounds of the formula I apparently only plays a minor role in the outcome of the syntheses, even if compared with the corresponding known perchlorates, which is highly surprising and advantageous. The com-pounds of the formula I are characterized, inter alia, for example, by determining their melting point and recording their IR absorption spectrum.
Thé invention is illustrated in more detail by the examples which follow.
Example 1 In a stirred apparatus, 54 ml (0.6 mol) of phosphorus oxychloride are slowly added dropwise to 73.9 g (1.0 mol) of dimethylformamide (DMF) with stirring and cooling at such a rate that the temperature of the reaction mixture does not exceed 20C. The resulting ~olution is cooled to -10C, and 30 g (0.2 mol) of p-hydroxyphenylacetic acid are added in portions with stirring. The resulting syrup-like mixture is first maintained at room temperature for 1 hour, then stirred at 60C for 2 hours and at 80C for 3 hours and then poured onto 500 g of ice. After the exothermic hydrolysis reaction resulting from the contact with the ice is complete, the resulting aqueous solution is stirred with activated carbon, filtered, and 38 g (0.22 mol) of sodium hexafluorophosphate, dissolved in 60 ml of water, are added to the clear solution obtained.
A light yellow precipitate is formed immediately, subse-quently separated off, washed with water and dried. It consi~ts of the compound of the formula I l-dimethyl-,,, ,,, , . , , ~ .
, ~ ' "
, ., , ~005330 amino-3-dimethylimino-2-[4-hydroxyphenyl]-1-propene hexafluorophosphate, m.p.: 198-199C.
The yield is 62.5 g (= 86% of theory).
The compound can be obtained analytically pure by recrys-tallization from methanol/diethyl ether (6:4 v/v) and has the following characteristics. m.p.: 212C (incipient decomposition). The IR spectrum can be seen from Figure 1.
Example 2 Example 1 is repeated, except that 53 g (0.23 mol) of sodium naphthalene-2-sulfonate, dissolved in 1.2 1 of water, are added instead of 38 g (0.22 mol) of sodium ~ hexafluorophosphate, dissolved in 60 ml of water, to the clear aqueous solution obtained. A light yellow precipit-ate is formed immediately, subsequently separated off, washed with water and dried. It consists of the compound of the formula I l-dimethylamino-3-dimethylimino-2-[4 hydroxyphenyl]-l-propene-naphthalene-2-sulfonate, m.p.:
262-263C.
The yield is 69 g (= 81~ of theory).
The compound can be obtained analytically pure by recrys-tallization from methanol and has the following charac-teristics. m.p.: 268C (incipient decomposition). The IR
spectrum can be seen from Figure 2.
Example 3 Example 2 is repeated, except that the same amount of sodium naphthalene-l-sulfonate instead of sodium naph-thalene-2-sulfonate is added. The light yellow precipit-ate formed is separated off, washed with water and dried.
It consists of the compound of the formula I l-dimethyl-amino-3-dimethylimino-2-[4-hydroxyphenyl]-l-propene .. ..
.
.. . . . . .
', ~0~)5330 naphthalene-l-sulfonate, m.p.: 235-237C.
The yield is 38.5 g (= 41~ of theory).
The compound can be obtained analytically pure by recrys-tallization from methanol and has the following charac-teristics: m.p.: 248C (incipient decomposition). The IRspectrum can be seen from Figure 3.
, , . , ~ .
~ , - :
.; .
- - Description Explosion-proof 1-dimethylamino-3-dimethylimino-2-aryl-l-propene salts, proces3es for their preparation and their use As is known, 1-dimethylamino-3-dimethylimino-2-aryl-1-propene perchlorates are important intermediates for the synthesis of heterocycles, such as, for example, pyrimi-dines (cf. Zaschke, Z. Chem. 17 (1977) p. 63 and 293;
Arnold, Collect. Czech. Chem. Commun. 38 (1978) 1371;
Zaschke, J. prakt. Chemie 321 (1979) 619) and pyridines (cf. C.A. 109:64513w, (1988)). Preparative methods for this class of compounds, which is also known by the short name trimethine perchlorates, are also known. It is furthermore known that these perchlorates, which are - slightly soluble in water, are explosive to highly explosive products when dry (cf. Chem. Eng. News 52 (1974) No. 31, p. 3), the handling of which in their possible use as intermediates is extremely dangerous.
~heir industrial use is therefore virtually precluded.
Accordingly, the ob~ect of the present invention was to provide trimethine salts which can be handled in an explosion-proof manner, can be prepared without difficul-ties in the purity required, and can otherwise be usedlike the perchlorates, but without risk of explosion, as intermediates, inter alia, for the syntheses of the abovementioned heterocycles.
Surprisingly, it has now been found that, while avoiding the use of perchlorate as anion, explosion-proof trimeth-ine salts of low to slight solubility in water can be obtained by reacting water-soluble trimethine salts in aqueous medium with non-oxidizing acids which can form trimethine salts of low to slight solubility in water and are inert towards the trimethine cation, or with water-soluble salts of these non-oxidizing acids and isolating , : , . . . .
- , ,, .. . ..
,, .:. ,, . , . :
"
~005330 . -- 2 --the trimethine salts of low to slight solubility which precipitate in the aqueous phase, preferably by filtra-tion or by centrifugation, and, if desired, purifying them further by washing and/or, if desired, by reprecipi-tation and, if desired, drying them.
The invention accordingly relates to explosion-proof trimethine salts of low to slight solubility in water which have the formula I
,~CH-N(cH3)2 R^C (+) X( ) (I) CH=N(cH3)2 in which R and X have the following meaningss R is aryl or heteroaryl which are unsubstituted or mono-or polysubstituted by halogen, (C1-C~)-alkyl, (C1-C12)-alkoxy or hydroxyl, in which aryl is preferably phenyl, naphthyl, biphenylyl, anthracenyl or tetra-linyl and heteroaryl is preferably pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, halogen is preferably F, Cl or Br, in particular F or Cl, and the radic~ls (C1-C12)-alkyl and (C1-C12)-alkoxy are unsubstituted or mono- or polysubstituted by halo-gen, in particular F or Cl;
X is the anion equivalent of a non-oxidizing acid radical which is inert towards the trimethine cation and can form trimethine salts of slight solubility in water, preferably from the group p-toluenesulfonate, naphthalene-2-sulfonate, naphthalene-l-sulfonate, naphthalene-1,5-disulfonate, BF4~-), SbF8~-), PF5(-), AlF6~-), in particular PF6(-) and naphthalene-2-sul-fonate.
The invention furthermore relates to a process for the preparation of explosion-proof trimethine ~alts of the abovementioned formula I by formylation of compounds of , . . . . . .
.
, ',: . ' , . : .
.. ..
- 200s~30 the formula II
R-CH2-COOH (II) in which R is as defined in formula I under the condi-tions of the Vilsmeier-Haack reaction, followed by hydrolysis of the formylation product in aqueous medium with the formation of water-soluble primary trimethine salts, which comprises adding mono- or polybasic acids of the formula III
(H)nX (III) in which X is as defined in formula I and n is a number from 1 to 3, preferably 1 or 2, in particular 1, or water-soluble salts thereof in at least stoichiometric amounts to the aqueous reaction mixture containing the ~ater-soluble primary trimethine salts and separating off - 15 the resulting trimethine salts of the formula I, of slight solubility in water, in a preferably fine-crystal-line form.
Preferred acids of the formula III or water-soluble salts thereof are p-toluenesulfonic acid, sodium p-toluene-sulfonate, sodium tetrafluoroborate, sodium hexafluoro-antimonate, sodium hexafluorophosphate, sodium hexa-fluoroaluminate, naphthalene-2-sulfonic acid, sodium naphthalene-2-sulfonate, sodium naphthalene-l-sulfonate, disodium naphthalene-1,5-disulfonate, or mixtures of these salts or scids, in particular with the acids or salts based on them. Hexafluorophosphate and naphthalene-2-sulfonate are particularly preferred.
The trimethine salts of the formula I prepared according to the invention are preferably formed in a fine-crystal-line form and can be easily separated off from the motherliquor, washed with water and, if desired, subsequently dried, after which they are typically obtained in a purity of over 99%. To purify them further, they can, if , ' ' " ., ' ' ...... , ~ . : .
.
,, , . , , . . :
:, , ': ,' , . . .
",' " ' ', ' ' ' ,: , , . . ~ . , , , "" '., ' :
~005330 desired, additionally be recrystallized from suitable solvents, which is however, in general not necessary for their further use as intermediates for the synthesis of heterocycles, since they are already excellent synthetic components even without additional purification. Guiding tests in this direction have also shown that, when the compounds according to the invention of the formula I are used as starting materials for pyrimidine syntheses, the anion of the compounds of the formula I apparently only plays a minor role in the outcome of the syntheses, even if compared with the corresponding known perchlorates, which is highly surprising and advantageous. The com-pounds of the formula I are characterized, inter alia, for example, by determining their melting point and recording their IR absorption spectrum.
Thé invention is illustrated in more detail by the examples which follow.
Example 1 In a stirred apparatus, 54 ml (0.6 mol) of phosphorus oxychloride are slowly added dropwise to 73.9 g (1.0 mol) of dimethylformamide (DMF) with stirring and cooling at such a rate that the temperature of the reaction mixture does not exceed 20C. The resulting ~olution is cooled to -10C, and 30 g (0.2 mol) of p-hydroxyphenylacetic acid are added in portions with stirring. The resulting syrup-like mixture is first maintained at room temperature for 1 hour, then stirred at 60C for 2 hours and at 80C for 3 hours and then poured onto 500 g of ice. After the exothermic hydrolysis reaction resulting from the contact with the ice is complete, the resulting aqueous solution is stirred with activated carbon, filtered, and 38 g (0.22 mol) of sodium hexafluorophosphate, dissolved in 60 ml of water, are added to the clear solution obtained.
A light yellow precipitate is formed immediately, subse-quently separated off, washed with water and dried. It consi~ts of the compound of the formula I l-dimethyl-,,, ,,, , . , , ~ .
, ~ ' "
, ., , ~005330 amino-3-dimethylimino-2-[4-hydroxyphenyl]-1-propene hexafluorophosphate, m.p.: 198-199C.
The yield is 62.5 g (= 86% of theory).
The compound can be obtained analytically pure by recrys-tallization from methanol/diethyl ether (6:4 v/v) and has the following characteristics. m.p.: 212C (incipient decomposition). The IR spectrum can be seen from Figure 1.
Example 2 Example 1 is repeated, except that 53 g (0.23 mol) of sodium naphthalene-2-sulfonate, dissolved in 1.2 1 of water, are added instead of 38 g (0.22 mol) of sodium ~ hexafluorophosphate, dissolved in 60 ml of water, to the clear aqueous solution obtained. A light yellow precipit-ate is formed immediately, subsequently separated off, washed with water and dried. It consists of the compound of the formula I l-dimethylamino-3-dimethylimino-2-[4 hydroxyphenyl]-l-propene-naphthalene-2-sulfonate, m.p.:
262-263C.
The yield is 69 g (= 81~ of theory).
The compound can be obtained analytically pure by recrys-tallization from methanol and has the following charac-teristics. m.p.: 268C (incipient decomposition). The IR
spectrum can be seen from Figure 2.
Example 3 Example 2 is repeated, except that the same amount of sodium naphthalene-l-sulfonate instead of sodium naph-thalene-2-sulfonate is added. The light yellow precipit-ate formed is separated off, washed with water and dried.
It consists of the compound of the formula I l-dimethyl-amino-3-dimethylimino-2-[4-hydroxyphenyl]-l-propene .. ..
.
.. . . . . .
', ~0~)5330 naphthalene-l-sulfonate, m.p.: 235-237C.
The yield is 38.5 g (= 41~ of theory).
The compound can be obtained analytically pure by recrys-tallization from methanol and has the following charac-teristics: m.p.: 248C (incipient decomposition). The IRspectrum can be seen from Figure 3.
, , . , ~ .
~ , - :
Claims (3)
1. An explosion-proof trimethine salt of low to slight solubility in water which has the formula I
(I) in which R and X have the following meanings:
R is aryl or heteroaryl which are unsubstituted or mono- or polysubstituted by halogen, (C1-C12)-alkyl, (C1-C12)-alkoxy or hydroxyl, in which aryl is preferably phenyl, naphthyl, biphenylyl, anthracenyl or tetralinyl and heteroaryl is preferably pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, halogen is preferably F, Cl or Br, in particular F or Cl, and the radicals (C1-C12)-alkyl and (C1-C12)-alkoxy are unsubstituted or mono- or polysubstituted by halogen, in par-ticular F or Cl;
X is the anion equivalent of a non-oxidizing acid radical which is inert towards the trimethine cation and can form trimethine salts of slight solubility in water, preferably from the group p-toluenesulfonate, naphthalene-2-sulfonate, naphthalene-1-sulfonate, naphthalene-1,5-disul-fonate, BF4(-), SbF6(-), PF6(-), AlF6(-), in particular PF6(-) and naphthalene-2-sulfonate.
(I) in which R and X have the following meanings:
R is aryl or heteroaryl which are unsubstituted or mono- or polysubstituted by halogen, (C1-C12)-alkyl, (C1-C12)-alkoxy or hydroxyl, in which aryl is preferably phenyl, naphthyl, biphenylyl, anthracenyl or tetralinyl and heteroaryl is preferably pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, halogen is preferably F, Cl or Br, in particular F or Cl, and the radicals (C1-C12)-alkyl and (C1-C12)-alkoxy are unsubstituted or mono- or polysubstituted by halogen, in par-ticular F or Cl;
X is the anion equivalent of a non-oxidizing acid radical which is inert towards the trimethine cation and can form trimethine salts of slight solubility in water, preferably from the group p-toluenesulfonate, naphthalene-2-sulfonate, naphthalene-1-sulfonate, naphthalene-1,5-disul-fonate, BF4(-), SbF6(-), PF6(-), AlF6(-), in particular PF6(-) and naphthalene-2-sulfonate.
2. A process for the preparation of a trimethine salt of the formula I as claimed in claim 1 by formylation of compounds of the formula II
R-CH2-COOH (II) in which R is as defined in formula I under the conditions of the Vilsmeier-Haack reaction, followed by hydrolysis of the formylation product in aqueous medium with the formation of water-soluble primary trimethine salts, which comprises adding acids of the formula III
(H)nX (III) in which X is as defined in formula I and n is a number from 1 to 3, preferably 1 or 2, in particular 1, or water-soluble salts thereof in at least stoi-chiometric amounts to the aqueous reaction mixture containing the water-soluble primary trimethine salts and separating off the resulting trimethine salts of the formula I, of slight solubility in water.
R-CH2-COOH (II) in which R is as defined in formula I under the conditions of the Vilsmeier-Haack reaction, followed by hydrolysis of the formylation product in aqueous medium with the formation of water-soluble primary trimethine salts, which comprises adding acids of the formula III
(H)nX (III) in which X is as defined in formula I and n is a number from 1 to 3, preferably 1 or 2, in particular 1, or water-soluble salts thereof in at least stoi-chiometric amounts to the aqueous reaction mixture containing the water-soluble primary trimethine salts and separating off the resulting trimethine salts of the formula I, of slight solubility in water.
3. Use of a trimethine salt of the formula I as claimed in claim 1 or prepared as claimed in claim 2 as intermediate for the synthesis of heterocycles, preferably of pyrimidines and pyridines.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3842062A DE3842062A1 (en) | 1988-12-14 | 1988-12-14 | EXPLOSION-SAFE 1-DIMETHYLAMINO-3-DIMETHYLIMINO-2-ARYLPROPEN-1 SALTS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DEP3842062.7 | 1988-12-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2005330A1 true CA2005330A1 (en) | 1990-06-14 |
Family
ID=6369135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002005330A Abandoned CA2005330A1 (en) | 1988-12-14 | 1989-12-13 | Explosion-proof 1-dimethylamino-3-dimethylimino-2-aryl-1-propene salts, processes for their preparation and their use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0449917A1 (en) |
| JP (1) | JPH04502158A (en) |
| KR (1) | KR910700227A (en) |
| CA (1) | CA2005330A1 (en) |
| DE (1) | DE3842062A1 (en) |
| NO (1) | NO912279D0 (en) |
| WO (1) | WO1990006913A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU759469B2 (en) * | 1998-04-24 | 2003-04-17 | Merck Sharp & Dohme Corp. | Process for synthesizing cox-2 inhibitors |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288784A (en) * | 1966-04-11 | 1966-11-29 | Monsanto Co | Method of preparing substituted chlorominium salts |
| US3993656A (en) * | 1974-11-19 | 1976-11-23 | Merck & Co., Inc. | 1,8-Naphthyridine compounds |
| US4310670A (en) * | 1980-02-26 | 1982-01-12 | Sterling Drug Inc. | Low-temperature, aqueous conversion of 4-picoline derivative to 5-cyano-[3,4'-bipyridin]-6(1H)-one |
| EP0036711B1 (en) * | 1980-03-22 | 1985-12-04 | Fbc Limited | Pesticidal heterocyclic compounds, processes for preparing them, compositions containing them, and their use |
| US4489011A (en) * | 1983-05-16 | 1984-12-18 | Merrell Dow Pharmaceuticals Inc. | Hypoglycemic N-(2-substituted-3-dialkylamino-2-propenylidene)-N-alkylalkanaminium camsylate salts |
-
1988
- 1988-12-14 DE DE3842062A patent/DE3842062A1/en not_active Withdrawn
-
1989
- 1989-12-09 EP EP90900851A patent/EP0449917A1/en not_active Withdrawn
- 1989-12-09 WO PCT/EP1989/001510 patent/WO1990006913A1/en not_active Application Discontinuation
- 1989-12-09 KR KR1019900701770A patent/KR910700227A/en not_active Application Discontinuation
- 1989-12-09 JP JP90501459A patent/JPH04502158A/en active Pending
- 1989-12-13 CA CA002005330A patent/CA2005330A1/en not_active Abandoned
-
1991
- 1991-06-13 NO NO912279A patent/NO912279D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0449917A1 (en) | 1991-10-09 |
| NO912279L (en) | 1991-06-13 |
| DE3842062A1 (en) | 1990-06-28 |
| WO1990006913A1 (en) | 1990-06-28 |
| KR910700227A (en) | 1991-03-14 |
| JPH04502158A (en) | 1992-04-16 |
| NO912279D0 (en) | 1991-06-13 |
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