GB692265A - Improvements in or relating to dichloracetamides - Google Patents
Improvements in or relating to dichloracetamidesInfo
- Publication number
- GB692265A GB692265A GB1262250A GB1262250A GB692265A GB 692265 A GB692265 A GB 692265A GB 1262250 A GB1262250 A GB 1262250A GB 1262250 A GB1262250 A GB 1262250A GB 692265 A GB692265 A GB 692265A
- Authority
- GB
- United Kingdom
- Prior art keywords
- amino
- chloral
- cyanhydrin
- diol
- dioxane
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Stereoisomeric compounds, or mixtures thereof, of the general formula <FORM:0692265/IV (b)/1> (wherein R1 and R2 each represent hydrogen or jointly represent a group -CHR4- in which R4 represents hydrogen, an alkyl group of not more than 4 carbon atoms or an aryl group, and R3 represents hydrogen or a nitro group) are manufactured by reacting the corresponding compounds containing a free amino group with choral cyanhydrin, or a precursor therefor, in the presence of an acid-binding agent. Convenient precursors for chloral cyanhydrin are chloral or chloral hydrate together with an alkali metal cyanide catalyst (preferably in a quantity less than one molecular equivalent of the reacting amine). When chloral cyanhydrin itself is used it may first be reacted with an acid-binding agent and the amine treated with the product obtained (which probably contains dichloropyruvonitrile, since this compound has been shown to be capable of effecting the dichloracetylation, though with inferior yield). The reaction may be effected in aqueous or non-aqueous media, advantageously at 0-25 DEG C. with chloral cyanhydrin itself or at 60-100 DEG C. with a precursor. Suitable acid-binding agents are inorganic bases, tertiary organic bases, excess of the reacting amine, or excess of the alkali metal cyanide when used. The process is applicable particularly to the preparation of chloramphenicol from D-threo-2-amino-1-p-nitrophenylpropane-1 : 3-diol, and the preparation of L- and DL-erythro-2-dichloracetamido-1-p-nitrophenylpropane-1 : 3-diol which are useful as intermediates for chloramphenicol and its racemate. In examples: (1) DL-erythro-5-amino-4-phenyl-2-methyl-1 : 3-dioxane is heated with chloral hydrate in aqueous solution in the presence of calcium carbonate and sodium cyanide; (2) the calcium carbonate in (1) is replaced by sodium acetate and part of the water by dioxane; (3) DL-erythro-2-amino-1-p-nitrophenylpropan-1 : 3-diol is treated as in (1); (4) and (9) the calcium carbonate in (3) is replaced by magnesium oxide, and (5) by sodium carbonate; (6) the sodium cyanide in (5) is replaced by potassium cyanide; (7) the starting material of (5) is replaced by the L-isomer; (8) the sodium carbonate in (5) is replaced by excess of potassium cyanide; (10) p DL-threo-2-amino - 1 - p - nitrophenylpropan - 1 : 3 - diol is heated with chloral hydrate, pyridine (or dioxane) and sodium cyanide; (11) DL-erythro-2 - amino - 1 - p - nitrophenylpropan - 1 : 3 - diol hydrochloride is agitated with chloral hydrate, sodium cyanide and pyridine in dioxane; (12) DL - erythro - 5 - amino - 4 - phenyl - 2 - methyl-1 : 3-dioxane is allowed to stand with chloral cyanhydrin, triethylamine and dioxane; (13) the DL-threo isomer is similarly treated; (14) DL - erythro - 5 - amino - 4 - phenyl - 2 - methyl-1 : 3-dioxane is dissolved in dilute hydrochloric acid, chloral cyanhydrin is added followed by caustic soda, and the suspension is allowed to stand; (15) DL-threo-2-amino-1-p-nitrophenylpropan-1 : 3-diol is allowed to stand with chloral cyanhydrin, triethylamine and dioxane; (16) the triethylamine in (15) is replaced by sodium carbonate; (17) chloral cyanhydrin is added to pyridine, and then DL-threo-2-amino-1-p-nitrophenylpropan-1 : 3-diol is added and the mixture heated; (18) DL - threo - 2 - amino - 1 - p - nitrophenylpropan-1 : 3-diol hydrochloride is dissolved in water, and chloral cyanhydrin is added followed by triethylamine; (19) L-erythro - 2 - amino - 1 - p - nitrophenylpropan - 1 : 3-diol hydrochloride is allowed to stand with chloral cyanhydrin, triethylamine and dioxane; (20) the DL-isomer (free base) is similarly reacted, but with a different order of mixing the reactants; (21) the hydrochloride of the DL-isomer is treated as in (19); (22) DL-erythro-2-amino - 1 - p - nitrophenylpropan - 1 : 3 - diol is allowed to stand with chloral cyanhydrin, sodium carbonate and pyridine; (23) and (24) DL-erythro-2-amino-1-phenylpropan-1 : 3-diol is allowed to stand with chloral cyanhydrin, triethylamine and dioxane; (24) chloral cyanhydrin is reacted with triethylamine in dioxane and the product is allowed to stand with DL-erythro - 2 - amino - 1 - p - nitrophenylpropan-1 : 3-diol. According to the Provisional Specifications, R1 and R2 in the general formula above may also represent acyl, lower alkyl or aralkyl groups or jointly a bivalent atom or group such as -CO-, -SO2- or -CR6R7-(where R6 and R7 represent hydrogen atoms or lower alkyl, cycloalkyl, aryl or aralkyl groups), whilst the benzene ring may be additionally substituted by halogen atoms or lower alkyl or alkoxy radicals. DL - Threo - and DL - erythro - 5 - amino - 4-phenyl - 2 - methyl - 1 : 3 - dioxane are obtainable by condensing bengaldehyde with 2-nitro-ethanol in the presence of sodium methoxide in methanol, liberating 2-nitro-1-phenylpropan-1 : 3-diol from its sodium salt so obtained, by the action of acetic acid in the presence of ether, separating the threo and erythro isomers by crystallization, condensing each with acetaldehyde in ether in the presence of an acid catalyst such as p-toluenesulphonic acid, and finally reducing the nitro group.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1262250A GB692265A (en) | 1950-05-19 | 1950-05-19 | Improvements in or relating to dichloracetamides |
ES0197917A ES197917A1 (en) | 1950-05-19 | 1951-05-18 | PROCEDURE FOR THE PREPARATION OF DICHLORACETAMIDES |
CY18059A CY180A (en) | 1950-05-19 | 1959-05-18 | Improvements in or relating to dichloracetamides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1262250A GB692265A (en) | 1950-05-19 | 1950-05-19 | Improvements in or relating to dichloracetamides |
GB1830850 | 1950-07-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB692265A true GB692265A (en) | 1953-06-03 |
Family
ID=26249147
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1262250A Expired GB692265A (en) | 1950-05-19 | 1950-05-19 | Improvements in or relating to dichloracetamides |
Country Status (2)
Country | Link |
---|---|
CY (1) | CY180A (en) |
GB (1) | GB692265A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1137446B (en) * | 1959-01-23 | 1962-10-04 | Chinoin Gyogyszer Es Vegyeszet | Process for the preparation of 1- (p-nitrophenyl) -2-dichloroacetyl-amino-1, 3-dioxypropane |
FR2417493A1 (en) * | 1978-02-20 | 1979-09-14 | Egyt Gyogyszervegyeszeti Gyar | N,N-di:substd. di:chloro:acetamide herbicide antidotes prepn. - by reacting chloral and sec. amine in aq. or polar organic medium in presence of e.g. a cyanide |
-
1950
- 1950-05-19 GB GB1262250A patent/GB692265A/en not_active Expired
-
1959
- 1959-05-18 CY CY18059A patent/CY180A/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1137446B (en) * | 1959-01-23 | 1962-10-04 | Chinoin Gyogyszer Es Vegyeszet | Process for the preparation of 1- (p-nitrophenyl) -2-dichloroacetyl-amino-1, 3-dioxypropane |
FR2417493A1 (en) * | 1978-02-20 | 1979-09-14 | Egyt Gyogyszervegyeszeti Gyar | N,N-di:substd. di:chloro:acetamide herbicide antidotes prepn. - by reacting chloral and sec. amine in aq. or polar organic medium in presence of e.g. a cyanide |
Also Published As
Publication number | Publication date |
---|---|
CY180A (en) | 1959-05-18 |
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