CA1068692A - N-carbamoyloxypyridinium salts and a process for their preparation - Google Patents

N-carbamoyloxypyridinium salts and a process for their preparation

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Publication number
CA1068692A
CA1068692A CA220,553A CA220553A CA1068692A CA 1068692 A CA1068692 A CA 1068692A CA 220553 A CA220553 A CA 220553A CA 1068692 A CA1068692 A CA 1068692A
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carbon atoms
general formula
alkyl
carbamoyloxypyridinium
pyridine
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French (fr)
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Peter Bergthaller
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE
N-carbamoyloxypyridinium salts of the general formula X?
are obtained when N-N-disubstituted carbamide chlorides are reacted with pyridine-N-oxides at temperatures between 0° and 40°C in aprotic solvents.
These compounds exhibit carboxyl activating properties making them useful in converting carboxylic acids into anhydrides in aqueous solution or into amides by means of reaction with suitable amines.

Description

This invention relates to N-carbamoyloxypyridinium salts and to a process ~or their preparation.
It is known that heteroaromatic bases such as pyridine, isoquinoline and quinoline can be converted into the corres-ponding ~-alkylpyridinium, isoquinolinium or quinolinium salts by reaction with alkylating agents.
It is also known that, when pyridine is reacted with acylhalides, extremely reactive N-acylpyridinium halides are formed which are much stronger acylating agents than the acid chlorides themselves. Acyl quinolinium salts are atypical in that, by the addition of suitable nucleophilic residues in the 2-positions, they can easily be converted into relatively~stable addition compolmds, the best known among which are the so-called Reissert compounds and also 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline which has become known in recent years as peptide reagent.
.
Carbamoyl pyridinium salts are also known, the best known being the stable compound diphenylcarbamoylpyridinium chloride. ~ !
In aqueous solution9 compounds with this type of ! .' .
; structure show carbo~yl activating properties enabling them to convert carboxylic acids into anhydrides in aqueou9 solution or into amide~ by means of suitable amines.
- Pyridine N-oxides are similar to pyridine in the case with which they can be reacted with alkylating agents to convert them into N-alkoxypyridinium ~alts, although the preparation of N-acyloxy pyridinium salts has previously remained limited to special cases. The reaction o~ pyridine-N-oxides with acid chlorides, anhydride~ or sulphoohlorides does not usually stop at the N-acyloxypyridinium salt stage ,- . ~ . : . .... .

1~6~369'~ ~
but proceeds to the incorporation of a nucleophilic residue and elimination of the N-oxide oxygen to form substituted pyridines. Reference should be .,., . ~ ~ I ~
made in this connection ~o E. Ochiai l'Aromatic Amine Oxides"~ Elsevier ;~:
1967 and A. Katrit~ky "Chemistry of Heterocyclic N-oxides" from the series "Organic Chemistry - a series of Monographs" Academic Press 1971 and to an article by K. Thomas and D. Jerchel in Angewandte Chemie 70, 719-146 (1958). It follows from this and from the documents quoted, that N-acyl- ' oxypyridinium salts are very difficult to isolate and extremely readily :~
attacked by nucleophilic residues.
It has now been found that N-carbamoyloxypyridinium salts of the .
general formula d ~ R

in whi ch R1 and R2 represent the same or different alkyl groups of 1 to 4 carbon atoms or phenyl groups or Rl denotes an alkyl group of 1 to 4 carbon atoms or a phenyl group and R2 denotes an alkylaminocarbonyl group `
wherein the alkyl moiety contains 1 to 4 carbon atoms, a dialkylamino-carbonyl group wherein each alkyl moiety contains 1 to 4 carbon atoms, acyl of 2 to 4 carbon atoms or alkoxycarbonyl of 2 to 4 carbon atoms, or R1 and R2 together represent the ring members for completing a pyrrolidine, -piperidine, perhydroazepine~ morpholi~e~ quinoline, dihydroindole or imidazolidone ring or the mem~ers required for completing a piperazine ring .
in which the second nitrogen atom estabishes the connection with a second similar molecular residue corresponding to the general formula set out above and which may be substituted with alkyl containing 1 to 4 aarbon atoms, R3, R4 and R5 represent hydrogen~ alkyl containing 1 to 4 carbon ~ . .
",,,,,, '.' : .

~68~9;2 atoms, halogen, cyano, alkoxy containing 2 to 4 carbon atoms, acylamino containing 2 to 4 carbon atoms or alkylureido wherein the alkyl group con-tains 1 to 4 carbon atoms, and X represents an anion. X preferably repre-sents an anion with weak nucleophilic character or basicity, in particular Cl , BF4 or C104 are obtained when N,N-disubstituted carbamide chlorides of the general formula '.,'.'~, ;, , ,. ~, ~ N - ~ - Cl .:, -. , ,. .: : -:, - ., in which R1 and R2 have the meanings indicated above, are reacted with pyridine-N-oxides of the general formula ' .
''.: ' :
R

~ 4 o~N~

R

in which R3~ R4 and R5 have the meanings indicated above at temperatures `
preferably between 0 and 40 C, more preferably between 0 and 20 C.
When R1 and R2 are alkyl groups they are in par~icular methyl, ethyl or isopropyl groups. Examples oP alkylaminocarbonyl and dia~kylamino-carbonyl groups within the defini~ion of R2iare methyl- and dimethylamino- `
carbonyl. When R2 i9 an acyl group it is for example an acetyl group.
Examples of alkoxycarbonyl groups represented by R2 are methoxy- and ethoxy-carbon~yl, groups~
Exarnples of alkyl groups within the definition of the groups R3, R4 and R5 are methyl and ethyl groups. Halogen is typically chlorine.
The reaction may in principle be carried out in almost any aprotic solvents and in some cases even in alcoholic or aqueous sytems, e.g. in : ,:

`''''' ' ' , :,, ;, , :
,, ., ,, . .. :, , , .... ,:, , . .. . . , : . .

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acetone, methylene chloride, ethyl acetate, dioxane, tetrahydrofuran, dime-thylformamide or ethanol, isopropanol, methyl glycol or ethanol/water. -~
The class of compounds comprising the N-carbamoyloxypyridinium salts is new and available in a surprisingly wide range of structural variations. Thus the carbamide chlorides which can be reacted with pyridine-N-oxides include simple N,N-dialkylcarbamide chlorides, carbamide chlorides derived from saturated heterocyclic amines, carbamide chlorides derived from aliphatic-aromatic secondary amines, aromatic carbamide chlorides as well as allophanic acid chlorides.

.. .
The pyridine-N-oxides may be substituted one or more times with alkyl, aryl, acylamino, alkoxyl or alkoxycarbonyl amino groups or halogen `~
but thcy should not carry any powerfully electrophilic substituents. 4-Nitropyridine-N-oxides, for example, cannot be reacted with carbamide chlo-rides.
The N-carbamoyloxypyridinium salts obtained vary in their stabili- --ty and resistance to hydrolysis according to the nature of the substituents -in the carbamide chloride or N-oxide used. The compounds derived from 2- ;
alkylpyridine-N-oxides and N,N-dimethylcarbamide chloride are particularly .
stable. ~ ~;
The pyridine-N-oxides used as starting materials are already known ~
and their preparation may be found in the literature summarized in "Aromatic -Amine Oxides~, Elsevier~1967.
Whereas most p~vridine-N-oxides are preferably prepared from the corresponding pyridines by peracid oxidation~ some speci~l representatives of this class of compounds, for .''~ ' ' .' .
' .. . ': ' "' `~:~ ',' ::' '"'''' . . ~

-5- ~ ;

. . . : . . ,:, -.. , .. : ,,, . . :. " ,' , . : ., ~ , . . :

1C~6~3~92 example the 2- and 4-alkoxypyridine N-oxides and 4-chloro- ~ -pyridine-N-oxide can be more easily obtained from the corresponding nitropyridine-N-oxides by nucleophilic exchange, e.g. with the corresponding alcoholates.
Special pyridine-N-oxides can also be obtained by reacting pyrylium salts with hydroxylamine, e.g. 2,4,6-trime;thylpyridine-N-oxide can be obtained from 2J4,6-trimethyl-pyrylium perchlorate and hydroxylamine ~A.Balaban and C.Nenitzescu, Annalen d.Ch. 625, pages 74).
N,N-Disubstituted carbamic acid chlorides are prepared by phosgenating the corresponding secondary amines. The allophanic acid chlorides can be prepared by the methods descrlbed by H.Ulrich, J.N.Tilley in J.Org. Chem. 29, 2401 (1964) and the methods described in German Offenlegungsschrift No. 2,008,116.
Preparation of the new carbamoyloxypyridinium salts is suitably carried out in aprotic media, e.g. in solvents such as acetone, methyl ethyl ketone, ethyl acetate, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, perchloroethylene, chlorobenzene, toluene, 1,2-dlmethoxyethane, 2,2-bls-methoxyethylether, N,N-dimethyl-formamide, tetrahydrofuran, dioxane or mixtures thereof.
In some cases it is even possible to use alcoholic or even aqueous solutions.
rrhe reaction temperature is not critical within the range of O to 40C although it has been found most suitable to employ reaction temperatures of 10 to 20C.
In indi~idual cases, reaction temperatures of up to 50C
can be employed without di~advantageous effects on the yield or purity of the reaction proclucts. The sequence in which the reactants are added is al~o not critical although purer products are generally obtained in the reaction of allophanic . ~ , . , .,, . . ........ .. . , , . . ................. . -, :
1~6869%

acid chlorides with pyridine-N-oxides, if pyridine-N-oxide is added to allophanic acid chloride.
The stoichiometric ratios of the reactants are generally also not critical although it has been found that t,he yields are almost never improved by using one of the two reactants in excess. The carbamoyloxy pyridlnium chlorides are generally obtained in yields of between 60 and ~5~ of the theory.
Exchange of the ionic chlorine formed in the reaction of carbamide chlorides for ~er, so-called hard anions in most cases does not entail any difficulties. Exchange against perchlorate or fluoborate is particularly advantageous since carbamoyl oxypyridinium perchlorates and fluoborates have a pronounced tendency to crystallisation, In some cases, the anion exchange can already be achieved at the preparation stage~by adding sodium perchlorate or the tetrafluoborate n alcohollc solution, to the reaction~mixture. This method is particularly advisable~if the N-carbamoyloxypyridinium chlorides are particularly sensitive to light or oontain groups which are easily split off by chloride, e,g. alkoxy groups, Another possibility is to dispense with the isolation or purification of the chlorides and treat the crude product with an aqueous or alcoholic solution of sodium tetrafluoborate or sodium perchlorate.
The N-carbamoyloxypyridinium salts of the invention are stable for considerable periods of time if moi~ture i~
excluded but their Ytability can be further improved by storing them at a low temperature. ~ome of these compounds, particularly the derivatives of carbamide chlorides in which ~-the group~ Rl and R2 are straight chain alkyl groups having two or more carbon atoms, tend to decompose on exposure to light. The compounds which are derived from carbamide A-G 1233 - 7 _ ,'''. ''' ',: ' ,' ', ' '' ' "' ' ''' " , ,` . ' "'" ,'' ' ' ' " ', ' "' ',' '" ',' ' " ' ~' ' ' ' " ' ~13 6~369~ :

chlorides are only slowly degraded in neutral aqueous solutions but the co~pounds derived from allophanic acid chlorides deco~pose rapidly under these conditions, in most cases within 1 to 10 hours.
The followin~ Table co~tains examples of compounds of the general formula which can be prepared by the process :according to the invention.
Available for the preparation are four methods A,B,C
and D which can be characterised as follows:
Method A:
The carbamoyloxypyridiniumchlorides are prepared by reactlng carbamide chlorides with pyridine-N-oxides in aprotic media.
Method B:
The carbamoyloxypyridinium chloride prepared according to method A lS subjected to salt conversion with so-called hard anion salts,e.g.~fluoborate or perchlorate.The salt conversion is carried out in an as far as possible anhydrous alcoholic solution.
Method C:
- ~ The carbamoyloxypyridinium chloride prepared according to method A is subjected to salt conversion in aqueous solution with alkali perchlorates or -tetrafluoroborates which are easily soluble in water. The alkali chloride remains dissolved and the carbamoyloxypyridinium perchlorate or -fluoroborate precipitatesD
Method D:
;The carbamoyloxypyridinium compounds are prepared by reacting the carbamide chlorides with the pyridine-N-oxides in protic solvents in the presence of salts which contain .. : ,. .. . .

~` ~

the above mentioned hard anions whereby the corresponding carbamoyloxypyridinium salts are precipitated nearly free from chloride.

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The N-carbamoyloxypyridinium salts of the inven-tion are valuable acylating agents with attenuated reactivity. -They are attacked comparatlvely non-selectively by nucleo-philic compounds. They are particularly reactive towards amino, thiol or hydroxyl groups and in aprotic solution they are also reactive with carboxyl groups which can react with them to undergo carboxyl activation.~
This reactivity enables N-carbamoyloxypyridinium salts to cross-link vegetable and animal proteins, in particular 1~ gelatine or similar binders of natural or synthetic origin which contain carboxyl or amino groups. They are also capable of modifying peptides.

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`` 1al613~92 Example 1 (Method A) 1 (Dimethylaminocarbonylox~)pyridinium chloride (Compound 1) 22 g oi dimethylcarbamide chloride (0.204 mol) are added dropwise to 19 g (0,2 mol) of pyridine-N-oxide in 100 ml of acetone at 0-15C. The colourless crystals which precipitate are suction filtered after 15 minutes; ~ -washed with acetone and dried under vacuum.
The yield is 36 g (89%) and the melting point i~ 163/167C
wlth decomposition.
Analysis: Galcula~ed C: 47.4 H: 5.43 N: 13.82 Cl: 17.5 on the basis of 8~I11N22Cl Found C: 47.1 II: 5.62 N: 1~.5 Cl: 17.0 :: :
Example 2 (Method B) 1 (Morpholine-_=carbonylo~ yridinium chloride (ComPound 15) 30~g of morpholine carbamide chloride in 50 ml of methylene chloride are added~dropwise with stirring to 19 g of pyridine-N-oxide (0,2 mol) in 100 ml of methylene chloride at 20C. After 60 minutes, 100 ml of acetone are added and ;~ ~ the reaction mixture is suction filtered, washed with ,:
acetone and dried in a vacuum with exclusion of light, For ~ -analysis the produc-t is recrystallised from ethanol/acetone and dried in a vacuum, The yield of crude product is 45 g (92~) and the melting to point is 104/106C with decomposition, When the same compound i~ prepared without the addition of acetone it is found to melt at 132C with deco~position, Analy~is: Calculated C: 45,7 H: 5.7 N: 10.7 Cl: 13.5 on the basis of CloHl3N2o3cl~o~ 5 H20 Found C: 45,8 H: 5,7 N: 10,8 Cl: 13,7 :
' ',~

6~36~2 ` ` "

xample 3 (Method B) 1 (Diethylaminocarbonylox~)-3=meth~lpyridinium perchlorate (Compound 11~
27 g (0.2 mol) of diethylcarbami~e chloride in 50 ml oL' ether are added dropwise with stirring to a solution of 22 g (0.2 mol) of 2-methylpyridine-N~oxide in 100 ml oI
ether at 0 to 10C, The reaction mixture is then stirred for a further 2 hours at 5C and cooled to 0C, The super-natant ether is decanted Irom the oil, and 36 g oI sodium perchlorate in ethanol are added. After the reaction mixture has been leIt to stand overnight, it lS SUCtlOIl Iiltered to remove the precipitated sodium chloride~ - -concentrated by evaporation in a vacuum at 30C and leIt to crystallise, The yield is 40 g (65% oI thé theory), and the melting point is 130 to 132C with decomposition.
,:,; ':

~ Exampl_ 4 (Method C) .
` ~ 1 (Morpholine carbonyloxy)pyridinium-fluoborate (ComPound 16) The solution oI 24.5 g (0.1 mol) of compound 15 is added to a solution oI 14 g of sodium Iluoborate in 25 ml of water. After 60 minutes, the reaction mixture is suction filtered. ~he yield is 25 g and the melting point is 138 to 140C with decomposition.
~::

Example 5 (Method C) l-(Morpholine carbonyloxy)pyridinium ~erchlorate (ComPound 17) 20 g of sodium perchlorate is added in as little water as possible to a solution of 24.5 g (0.1 mol) of compound 15 in 60 ml of water. The reaction mixture is left to stand for 30 minutes and then suction filtered.
The yield is 27 g and the melting point is 150 to 152C

with decomposition.
A-G 123~ - 25 -. '','''' ,'''' ',`'`''' `'`,'''' '' ~'"' ';'i' '','" :'' ;,"` ''.' ' ... . . . . . . . . . . . . . .

6~369Z

xample 6 (Method D) l-(Morpholine-N-carbonyloxy)-3-ethoxycarbonylaminopyridinium perchlorate (compound 34) 30 g (0.2 mol) of morpholinocarbamide chloride are added to 36,4 g (0.2 mol) of 3-ethoxycarbonylaminopyridine~N-oxide in 150 ml of isopropanol at room temperature. 30 g of sodium perchlorate in 150 ml of ethanol are added after 30 minutés and the reaction mixture is left to stand overnight.
The precipitated crystals are suction filtered.

The yield is 50 g and the melting point is 162 to 163 with decomposition, Example 7 (Method A) l-(Imidazolidone-N-carbonyl_xy)-pyridinium chloride (Compound 58) H ~ N - C - O - ~ C1 19 g of pyridine-N-oxide (0.2 mol) in 50 ml of methylene chloride are added dropwise at O to 10C to a solution of 29.7 g of imidazolidone-N-carbonyl chloride (0.2 mol) (prepared by the method of H.Ulrich et al., J.Org.Chem. 29, 2403) in 150 ml of methyIene chlo~de. After 30 minutes, the reaction mixture is suction filtered, washed with acetone and dried under vacuum.
The yield is 43 g (88%) and the melting point with decomposition is 221 to 223C

Analysis:Calculated C: 44.4~ H: 4.41~o N:17.7% Cl: 14,6 based on CgHloN3o3cl FoundC: 44,1% H: 4.1% N:18,0% Cl: 14.3 ` `' 16)6~6~9~ ~

Example 8 (Method A) l-(N,N~-Dimethylureido-N-carbonylo~y?-2-methyl-p ~ inium chloride (Compound 51) -' CH3NH-~-N ~ Cl ~ . .':.

22 g (0.202 mol) of 2-methylpyridine-N-oxide in 50 ml of methylene chloride are added dropwise at O to 10C to a solution of 30.1 g (0.2 mol) of N,N'-dimethyl-allophanyl chloride (prepared by phosgenating N,N~-dimethylurea by -the method of H.ulrich et al, J. Org. Chem. 29, 2402) in 150 ml of methylene chlorlde. The colourless crystals ~ ~
whlch preolpitate are suctlon filtered, washed with a little ~ ;
acetone and dried under vacuum.
The yield~is 41.5 g (ao~) and the melting point is 105C
with decompositlon). ;~ ~

, ~ ~
; Example 9 (Method A) ~ ~
20;~ (N-Nethoxycarbonyl-N-phenyl-carbon~lox~)-pyridinium chloride (Compound 60) -~-N-~-o- ~ C1 ~

21,3 g of N-methoxycarbonyl-N-phenyl-carbamide chloride in 200 ml of methylene chloride are added dropwise to a solution of 9.5 g (0.1 mol) of pyridine-N-oxide in 200 ml of methylene chloride at 0C. The crystal~ which precipitate are suction fil-tered and dried under vacuum.
The yield is 27 3 g (90~) and the melting point is 113-134C
with decomposition, A-~ 1233 - 27 -j~ .

Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. N-Carbamoyloxypyridinium salts of the general formula X?

wherein R1 and R2 represent the same or different alkyl groups of 1 to 4 carbon atoms or phenyl groups or R1 denotes an alkyl group of 1 to 4 carbon atoms, a phenyl group and R2 denotes alkylaminocarbonyl wherein the alkyl moiety contains 1 to 4 carbon atoms, dialkylaminocarbonyl, wherein each alkyl moiety contains 1 to 4 carbon atoms, acyl of 2 to 4 carbon atoms, alkoxycarbonyl of 2 to 4 carbon atoms, or R1 and R2 together represent the ring members required for completing a pyrrolidine, piperidine, perhydro-azepine, morpholine, quinoline, dihydroindole or imidazolidone ring or the members required for completing a piperazine ring in which the second nitrogen atom establishes the connection with a second similar molecular residue corresponding to the general formula set forth above and which may be substituted with alkyl containing 1 to 4 carbon atoms, R3, R4 and R5 represent hydrogen, alkyl containing 1 to 4 carbon atoms, halogen, cyano, alkoxy containing 2 to 4 carbon atoms, acylamino containing 2 to 4 carbon atoms or alkylureido wherein the alkyl group contains 1 to 4 carbon atoms, and X represents an anion.
2. A process for the preparation of N-carbamoyloxypyridinium salts of the general formula X?

wherein R1 and R2 represent the same or different alkyl groups of 1 to 4 carbon atoms or phenyl groups or R1 denotes an alkyl group of 1 to 4 carbon atoms or a phenyl group and R2 denotes an alkylaminocarbonyl group wherein the alkyl moiety contains 1 to 4 carbon atoms, a dialkylaminocarbonyl group wherein each alkyl moiety contains 1 to 4 carbon atoms, acyl of 2 to 4 carbon atoms or alkoxycarbonyl of 2 to 4 carbon atoms, or R1 and R2 together represent the ring members for completing a pyrrolidine, piperidine, per-hydroazepine, morpholine, quinoline, dihydroindole or imidazolidone ring or the members required for completing a piperazine ring in which the second nitrogen atom establishes the connection with a second similar molecular residue corresponding to the general formula set out above and which may be substituted with alkyl containing 1 to 4 carbon atoms, R3, R4 and R5 represent hydrogen, alkyl containing 1 to 4 carbon atoms, halogen, cyano, alkoxy con-taining 2 to 4 carbon atoms, acylamino containing 2 to 4 carbon atoms or alkylureido wherein the alkyl group contains 1 to 4 carbon atoms, and X
represents an anion, which comprises the step of reacting carbaminochlorides of the general formula wherein R1 and R2 have the meanings indicated above with pyridine-N-oxides of the general formula in which R3, R4 and R5 have the meanings indicated above at a temperature between 0° and 40°C, and optionally exchanging the ionic chloride formed in the reaction as X to another anion.
3. A process as claimed in claim 2 wherein an obtained chloride ion X is exchanged to provide as X a perchlorate or fluoroborate anion.
4. A process as defined in claim 2 for the preparation of N-carbamoyloxy-pyridinium tetrafluoroborates or perchlorates of the general formula according to claim 2, wherein X? represents BF4? or ClO4?, characterised in that the carbamido chlorides are reacted with pyridine-N-oxides in the presence of sodium fluoroborate or sodium perchlorate.
5. Process as defined in claim 2 for the preparation of N-carbamoyloxypyridinium tetrafluoroborates or perchlorates of the general formula according to claim 2, wherein X? represents BF4? or ClO4?, characterised in that carbamoyloxypyridinium chlorides of the general form-ula according to claim 1 are reacted with aqueous solutions of sodium tetra-fluoroborate or sodium perchlorate.
CA220,553A 1974-02-23 1975-02-21 N-carbamoyloxypyridinium salts and a process for their preparation Expired CA1068692A (en)

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JPS5950986B2 (en) * 1979-01-11 1984-12-11 富士写真フイルム株式会社 Photographic material with carboxylic acid polymer layer
JPS60222479A (en) * 1984-04-20 1985-11-07 Nippon Tokushu Noyaku Seizo Kk Tetrahydroquinolin-1-ylcarbonylimidazole derivative, its intermediate, their production and herbicide and fungicide therefrom
JPS6160682A (en) * 1984-08-30 1986-03-28 Nippon Tokushu Noyaku Seizo Kk Tetrahydroquinolin-1-ylcarbonylimidazole derivative, its intermediate, its production, herbicide, agricultural and horticultural fungicide
JPS61227506A (en) * 1985-04-01 1986-10-09 Nippon Tokushu Noyaku Seizo Kk Carbamoylimidazole, intermediate and, production thereof and herbicide, agricultural and horticultural fungicide
US4843163A (en) * 1987-12-02 1989-06-27 Smithkline Beckman Corporation Certain 3-(2-phenethyl)-1-carbamoyloxypyridinium halide intermediates
ATE385609T1 (en) * 1999-09-29 2008-02-15 Fujifilm Corp ELECTROLYTE COMPOSITION, PHOTOELECTRIC CONVERSION DEVICE AND PHOTOELECTROCHEMICAL CELL
CA2585645C (en) 2004-10-29 2014-10-21 Musc Foundation For Research Development Ceramides and apoptosis-signaling ligand
EP1814854B1 (en) * 2004-10-29 2015-02-25 MUSC Foundation For Research Development Cationic ceramides, and analogs thereof, and their use for preventing or treating cancer
CN102368905B (en) 2008-11-06 2015-04-01 南卡罗来纳医科大学研究发展基金会 Lysosomotropic inhibitors of acid ceramidase

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FR2262036B1 (en) 1979-04-20
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CH613694A5 (en) 1979-10-15
FR2262036A1 (en) 1975-09-19

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