GB2202535A - Process for the preparation of alpha -amino-and alpha -azido-n-acyl-2, 6- dimethylanilines - Google Patents
Process for the preparation of alpha -amino-and alpha -azido-n-acyl-2, 6- dimethylanilines Download PDFInfo
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- GB2202535A GB2202535A GB08806464A GB8806464A GB2202535A GB 2202535 A GB2202535 A GB 2202535A GB 08806464 A GB08806464 A GB 08806464A GB 8806464 A GB8806464 A GB 8806464A GB 2202535 A GB2202535 A GB 2202535A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
Abstract
Process for the preparation of the compounds of the general Formula (I) and salts thereof <IMAGE> [wherein X<1> is azido or amino and R is hydrogen, C1-4 alkyl or phenyl] which comprises reacting an aniline derivative of the general Formula (II> <IMAGE> [wherein X<2> is chlorine or bromine and R is hydrogen, C1-4 alkyl or phenyl] with alkali metal azide and if desired reducing a thus obtained azide of the general Formula (I) (wherein X<1> is azido and R is as defined above), preferably with a complex alkali hydride or by catalytic hydrogenation, to give the amine of general formula (I) (wherein X<1> is amino and R is as defined above) and if desired converting the obtained product to a salt by reaction with acid.
Description
PROCESS FOR THE PREPARATION OF AMINOACYL ANILINES
The present invention relates to a process for the preparation of the compounds of the formula (I)
and salts whereof, wherein
X1 stands for azido or amino groups, and
R stands for hydrogen, methyl or phenyl.
Only those compounds of the general Formula (I) are known from the literature, wherein
R stands for hydrogen or methyl or phenyl and
X stands for chlorine, bromine or amino group.
The compound wherein X1 stands for amino group is pharnacologically valuable. The pharmaceutically useful salts of this compound can be used for the treatment of ventricular tachycardia, arrythmia and condition after miocardial infarct gP.P. Sutton: Brit. J. Clin. Pharm., 1S, 530 (198n); W. Ryan et al.: Am. 3 Cardiol., 43, 285 (1979)7.
Several methods are disclosed in DOS 2 400540; C.A.
82, P 31 165e and other articles g E.W. Byrnes et awl. : 3.
Med. Chem., 22, 1171 (1979); P.A. Tenthorey et awl. : J.Med.
Chem., 24 798 (198l)J for the preparation of a compound of the general Formula (I), wherein X1 stands for amino group.
According to the above process the compound can be prepared from a compound of the general Formula (II)
- wherein
X2 stands for halogen (chlorine or bromine), and
R is as defined ahove.
A haloanilide of the general Formula (II) is reacted with ammonia by first forming a phthalimide derivative by Gabriel synthesis and by subjecting the obtained phthalimide derivative to hydrazinolysis, and forming an amino group by removing the phthalyl group.
The haloacyl anilide of the general Formula (II) is prepared by acylating an amine of the general Formula (III)
with haloacyl nalide of the Formula (IV)
in the presence of an acid binding agent such as sodium acetate in acetic acid ,tCN.Lofgren, C. Tenger: Acta Chem.
Scand., S, 1806 (1954) 7. The formation of the amino group by the above method has the following disadvantages: the direct ammonolysis can generally be performed only in a low conversion, which is for instance 28 % in case of R = CH3, and 10 % in case of R = phenyl, and the reaction can be accompanied by the formation of undesired higher amines next to the primary amine
When carrying out the reaction through phthalimide intermediate, a toxic compound:hydrazine is used in order to carry out dephthalylization (G.D.Muir: Hazard in the
Chemical Laboratory, London, The Chemical Society, 1977, o.
277).
According to the invention conpounds of th 3 general Formola (I) and salts tharnof - wherein X1 stands for azido or amino group,
R stands for hydrogen, C14 alkyl or phenyl can be prepared by reacting an aniline derivative of the general Formula (II)
- wherein
X2 stands for chlorine or bromine and
R stands for hydrogen, alkyl or phenyl with an alkali metal azide, and if desired reducing the obtained compound of the general Formula (I) - wherein X1 stands for azido group and R is as give above - preferably by using a complex alkali hydride or by catalytic hydrogenation, and converting if desired the product into salt by using an acide. R, X1, x2 are as given above.
According to our experiences the preparation of azido acyl compounds from haloacyl compounds can be carried out by using alkali metal azides, preferably sodium azide, in an aqueous or aqueous organic solvent mixture, preferably in aqueous methyl, ethyl or propyl alcohol, or in the presence of ethylene glycol eemiethers (I-r.Fthyl or ethyl). The compounds of the general Formula (I; - wherein R stands for hydrogen, methyl or phenyl and X1 stands for azido - can be formed during the reaction in a good yield (70-90 %) in a pure form without cide products.
The compounds of the general Formula (I) - wherein x1 stands for azido group - can be reduced by known methods ,rith complex metal hydrides, preferably with sodium borohydride, in an alcoholic solution, preferably in ethanol r. Sheradsky: Azides as Synthetic Starting Materials, in S.
Patai (ed.): The Chemistry of Functional Group, The
Chemistry of Azido Group, Wiley-Interscience, New York, 1971, 6., p 331J, or by known methods by catalytic hydration /M. Freifelder: Catalytic Hydrogenation in Organic
Synthesis, Procedures and Commentary, Wiley-Interscience,
New York, 1978, p 1387.
The product of the reduction is a pure amino compound of the general Formula (I), wherein X1 stands for amino. The preparation of the azido compound and the amino compounds can be prepared in a simple apparatus and the reaction and the workup of the mixture can be well monitored by thin layer chromatography.
The preparation of the compounds of the general
Formula (I) by the new process according to the invention has the following advantages: 1/ The formation of the optimal amino group from the point
of view of the pharmacological activity can be performed
by a simple method without using any special equipment
at atmospheric pressure.
2/ The reactions result in a pure product in a good yield.
3/ The starting materials of the products are readily
accessible and are not detrimental for health.
The details of the invention are further illustrated by the following non-limiting compounds.
Example l/a.
2,6-dimethyl- -azido-acetanilide (Compound of the general Formula (I), R=H, X1=N3)
To a solution of 5.91 g (0.03 mole) 2,6-dimethyl- t - chloro-acetanilide in 50 ml acetone an aqueous solution of 2.93 g (0.045 mole) sodium azide in 10 ml water is added.
The reaction mixture is boiled under reflux at the boiling point of the solvent mixture. The reaction is monitored by thin layer chromatography (Kiesel gel 60 F 254, on 0.2 mm layer in a 1:1 mixture of choroform and ether). The mixture is worked up after 5 hours boiling. The solvent is distilled off on water bath under 2666 Pa vacuo and 15 ml water and 25 ml chloroform are added to the residue, the organic layer is separated and the aqueous layer is shaken out twice with 20 ml chloroform. The combined organic solutions are dried above sodium sulphate, filtered, and the filtrate is evaporated to dryness on water bath under 266 Pa vacuo. The residue is dissolved in 50 ml ether and upon cooling tne product crystallizes. The product is filtered and dried.
Yield: 4.45 g (72.7 %).
Analysis C10H12N40 (mol. weight = 204.24)
Calculated: C 58.81, H 5.92, N 27.43 %,
Found:
C 58.62, H 5.88, N 27.33 %.
IR (nujolt: 3200-3300 (NH), 2090 =h3), 1650 (CONH) cam~1.
Example l/b.
2,6-dimethyl-t -azido-acetanilide
To a solution of 3.95 g (0.02 mole) 2,6-dimethyl-t chloro-acetanilide in 50 ml dimethyl formamide an aqueous solution of 1.95 g (0.03 mole) sodium azide in 10 ml water is added and the mixture is kept for 4 hours at 50-60 OC.
The reaction is monitored by thi.n layer chromatography (Kiesel gel 60 F 254, 0.2 mm layer, in a 1:1 mixture of chloroform and ether). The solvents are distilled off at reduced pressure (266.6 Pa), 50 ml water are added to the residue and the mixture is shaken out with chloroform (3x50 ml). The organic solution is dried above sodium sulphate, filtered and evaporated (2666 Pa). The residue is dissolved in ether, cooled and the precipitated crystalline base is filtered, washed with an 1:1 mixture of ether and n-hexane and dried. Yield 2.95 g (72.3 %). Meltng point 86-88 OC.
The physical constants and spectral data of the product are identical with the data of the product of Example l/a.
Example 2/a.
2,6-dimethyl-t -azido-propionyl anilide (Compound of the general Formula (I), R=CH3, X1=N3) fs a solution of 7.68 g (0.03 mole) 2,6-dimethyl-~ bromo-propionyl-anilide in 100 ml acetone an aqueous solution of sodium azide (2.93 g, 0.05 mole) in 10 ml water is added, and the reaction mixture is boiled for 2 days. The reaction is monitored by thin layer chromatography (Kiesel gel 60 F 254 on 0.2 mm layer developed in a 9:l mixture of carbon tetrachloride and ether). The solvent is distilled off at reduced pressure (2666 Pa), the residue is dissolved in 50 ml ether and the mixture is diluted with n-hexane until crystallization (10 ml). Upon cooling the product is filtered, yield 5.98 (91 %), melting point 78-80 OC.
Analysis C1lHl4N40 (218.26)
Calculated: C 60.54, H 5.47, N 25.67 %,
Found: C 60.60, H 6.70, N 25.88 %.
IR (nujol): 3200-3350 (NH), 2100 (N3)m 1650 (CONH) cm'1 Example 2/b.
2,6-dimethyl- < -azido-propionyl-anilide
To solution of 5.12 g (0.02 mole) 2,6-dimethyl-t bromo-propionyl-anilide in 20 ml dimethyl formamide an aqueous solution of 1.95 g (0.03 mole) sodium azide In 10 ml water is added, whereafter the product is prepared as disclosed in Example l/b. Yield 3.95 g (90 %), melting point 7e.80 OC.
The physical constants and the spectral data of the product are identical with the data of the product of
Example 2/a.
Example 2/c.
2,6-dimethyl- X -azido-propionyl-anilide
To a solution of 5.12 g (0.02 mole) 2,6-dimethyl-- bromo-propionyl-anilide in 30 ml ethylene glycol monomethyl ether a solution of 1.95 g sodium azide is added in 10 ml water and the reaction mixture is kept for 6 hours at 60 OC.
The mixture is cooled to room temperature, diluted with water with the 100 ml of water and shaken out with 3x50 chloroform. The chloroform solution is dried above sodium sulphate, filtered an evaporated at reduced pressure (2666 Pa). The residue is dissolved in 20 ml ether and diluted with n-hexane until crystallization. Yield 3.55 g ((81 %). The physical constants and the spectral data of the product are identical with those of the product of Example 2/a.
Example 3/a.
2,6-dimethyl- -azido-r -phenyl-acetanilide (general Formula I, R=Ph, X1=N3)
To a solution of 8.21 g (0.03 mole) 2,6-dimethyl-t - chlcro-x; -phenyl-acetanilide in 100 ml acetone solution an aqueous solution of 2,93 g (0.045 mole) sodium azide is added in 10 ml water and the reaction mixture is boiled for 2 days. The reaction is monitored by thin layer chromatography (Kiesel gel 60 F 254, 0.2 mm layer in a 16:1 mixture of chloroform and ether). The product is worked up and crystallized according to Example l/a.
Yield: 6.40 g (76 '), melting point: 139-140 OC.
Calculated: C 68.56, H 5.75, N 19.99 %,
Found: C 68.43, H 5.88, N 20.08 %.
IR (nujol): 3100-3300 (NH), 2070 (N3), 1635 (CONH) cm 1 Example 3/b.
2,6-dimethyl-X -azido--r -phenyl-acetanilide
To a solution of 5.46 g (0.02 mole) 2,6-dimethyl-4 chloro-lx; -phenyl-acetanilide in 20 ml dimethyl formamide a solution of 1.95 g (0.03 mole) sodium azide in 10 water is added. The reaction mixture is worked according to Example l/b. Yield 3.0 g (73.5 %), melting point 139-140 OC. The physical constants of the product correspond to the product of Example 3/a.
Example 4/a.
2,6-dimethyl-z -amino-acetanilide (general Formula I, R=H, X1=NH2) To a suspension of 1.65 g (0.044 mole) sodium borohydride in 100 ml anhydrous isopropyl alcohol a solution 4.08 g 2,6-dimethyl-oc-azido-acetanilide (0.02 mole) in 50 ml isopropyl alcohol is added under stirring. When the addition is completed and the cooling is ceased, the mixture warmed up to room temperature is boiled for 18 hours, while the reaction is monitored by thin layer chromatography (Kiesel gel 60 F 254, 0.2 mm layer, in an 1:3 mixture of chloroform and tetrahydrofuran). The solvent is distilled off at reduced pressure (2666 Pa) upon heating on water bath. To the residue a 10 % diluted hydrochloric acid is added, and the mixture is extracted with chloroform (3x50 ml).The acid aqueous solution is alkalized with a diluted alkali (NaOH or a 10 % solution of KOH), and shaken out with 3x50 ml chloroform. The chloroform solution is dried above sodium sulphate, filtered and evaporated. The residue is dissolved in 30 ml ether, cooled, and the precipitated filters are filtered and dried. Yield: 2.3 g (65 %), m.p.: 81-83 OC.
Analysis C10H14N20
Calculated: C 67.39, H 7.92, N 15.72 %,
Found: C 67.21, H 8.08, N 15.59 95.
IR (nujol): 3150-3350 (NH, NH2), 1645 (CONH) cm1.
1.78 g (0.01 mole) base is dissolved in 15 ml ethanol saturated with hydrochloric acid while warm (about 30-40 OC), the mixture is cooled to room temperature and diluted with ethyl ether until crystallization, and is placed in a refrigerator. The hydrochloride salt of the product is filtered the next day, washed with ether and dried.
Yield: 1.98 g (52 %), melting point: 294-296 OC.
Analysis C10H14N20.HCl (214.71)
Calculated: C 55.95, H 7.04, 31 13.05, Cl 16.51 %,
Found: C 55.94, H 7.08, N 13.18, C1 16.23 %.
Example 4/b.
2,6-dimethyl-X -amino-acetanilide
To a solution of 1.97 g (0.01 mole) 2,6-dimethyl-tt azido-acetanilide in 40 ml ethanol about 0.7 g palladium on charcoal catalyst is added, whereafter hydrogen is passed through the reaction mixture under stirring at room temperature. The reaction is monitored by thin layer chromatography as in Example 4/a and the reaction is completed within about 4 hours. The catalyst is filtered off, the filtrate is heated on water bath and evaporated at reduced pressure (2666 Pa). The residue is dissolved in 20 ml chloroform and it crystallizes upon dilution with ether.
Yield: 1.87 g (87 %), melting point: 81-83 OC.
Analysis on the calculated analysis values in Example 4/a.
for the Formula C1oHl4N20: found data: C 67.33, H 7.89, N 15.88 95.
Example 4/c.
2 ,6-dimethyl-oc -amino-acetanilide
Catalytic hydrogenaticn is carried out according to
Example 4/b. After the filtration of the catalyst the filtrate is evaporated to about half volume at reduced pressure (2666 Pa), and to this ethanolic solution hydrochloric acid gas is introduced until pH=3, and after dilu tio, .sith ether directly the hydrochloride salt of the product is obtained. Yield: 1.95 g (91 %), melting point: 295296 OC. Calculated analysis data, see Exaple 4/a. Found for the hydrochloride salt: C 55.98, H 7.12, N 12.98 %.
Example 5/a 2 ,6-dimethyl-oO -amino-propionyl-anilide (Formula I, R=CH3, X1=NH2)
A solution of 3.27 g (0.015 mole) 2,6-dimethyl-oc- azido-propionyl-anilide in 30 ml isopropyl alcohol is added to a suspension of 1.26 g (0.033 mole) sodium azide in 30 ml isopropyl alcohol cooled to O C under stirring. When the cooling is ceased, the mixture is boiled for 18 hours and during the reaction thin layer chromatography is used to monitor the reaction (Kiesel gel 60 F 254, 0.2 mm layer, in a 1:3 mixture of chloroform and tetrahydrofuran) . The workup is performed according to Example 4/a. Yield: 2.45 g (85 95), melting point: 208-209 OC.
Analysis C11H16N20 (192.26)
Calculated: C 68.72, H 8.39, N 14.57 %,
Found: C 68.79, H 8.46, N 14.63 %.
IR (nujol): 3100-3300 (NH, NH2), 1650 (CONH) cm-1 1.92 g (0.01 mole) base is dissolved in 10 ml ethanol saturated with hydrochloric acid gas. The mixture is diluted with ether until crystallization. In the cooled solution the precipitated crystals are filtered, washed with ether and dried. The hydrochloride salt of the product is obtained with a yield of 2.06 g (90 %), melting point: 152154 OC.
Analysis CllHl6N20.HCl (228.73)
Calculated: C 57.77, H 7.49, N 12.25, C1 15.50 %,
Found: r 57.68, H 7.63, N 12.28, C1 15.53 %
IR (nujol): 3230 (NH), 3000-2800 (N+H3), 1665 (CONH) cm1.
Example 5/b.
2,6-dimethyl-α.amino-propionyl-anilide 2.18 g (0.01 mole) 2,6-dimethyl-X -azido-propionylanilide is added to a suspension of 0.82 g (0.022 mole) sodium borohydride in 20 ml ethanol, cooled to -20 C under stirring. After 30 minutes the mixture is allowed to warm up to room temperature, whereafter the mixture is boiled under reflux at the boiling point of the solvent mixture for 14 hours. The solvent is removed by distillation at reduced pressure (2666 Pa), and 15 ml of water is added to the residue and shaken out with 3x25 ml chloroform. The organic solvent part is dried above sodium sulphate, filtered an evaporated to dryness. The residue is dissolved in 5 ml chloroform, diluted with ether until the formation of crystals.The crystalline product is filtered from the cooled solution, washed with ether and dried. The physical constants and the spectral data of the base are identical with the data of the product according to 5/b. Yield: 1.58 g (82 %).
Example 5/c.
2,6-dimethyl-oc -amino-propionyl-anilide
To a solution of 4.36 g (0.02 mole) 2,6-dimethyl-t azido-propionyl-anilide prepared by any çf the previous examples 3/a, b, in 100 ml methanol 1.2 g palladium on charcoal catalyst is added and the hydrogenation is carried out according to Example 4/b, and the reaction is monitored by chromatography. The reaction mixture is filtered and concentrated to 20 ml at reduced pressure (2666 Pa). The alcoholic solution is acidified to pH-2 by introducting hydrochloric acid gas, and it is diluted with ether until the first crystals crystallize and the mixture is cooled. The hydrochloride salt of the proruct is filtered, washed with ether and dried. Yield: 3.3 g (86 %).The physical constants and the spectral data of the product are identical with the data of the product of Example 5/a.
Example 5/d.
2,6-dimethyl-oc -amino-propiongl-anilide To a solution of 6.54 g (0.03 mole) 2,6-dimethyl-t azido-propionyl-anilide in 150 ml ethanol at room temperature 1.8 g palladium on charcoal catalyst is added and hydrogenation takes place under shaking. The hydrogenation is monitored by thin layer chromatography (Kiesel gel 60 F 254, on 0.2 mm layer developed in a 9:1 mixture of chloroform and methanol). The hydrogenation is completed within about 6 hours. The catalyst is filtered, the filtrate is evaporated at reduced pressure (2666 Pa), and the residue is dissolved while hot (40 OC) in ethanol saturated with hydrochloric acid (20 ml). The solution is cooled and diluted with ether until the first crystals crystallize. The crystalline hydrochloride salt is filtered, washed with ether and dried.Yield: 5.1 g (88.5 %). The physical constants and spectral data of the product are identical with the data of the product of Examples 5/a, c.
Example 6/a.
2 ,6-dimethyl- Oc-amino- Oc-phenyl-acetanilide (Compound of the Formula I, R=Ph, X1=NH) A solution of 5.60 g (0.02 mole) 2,6-dimethyl- - azido- IX -phenyl-acetanilide in 50 ml isopropyl alcohol is added to a suspension of 1.65 g (0.044 mole) sodium borohydride in 50 ml isopropyl alcohol cooled to O OC under stirring. When the addition is completed, the mixture is allowed to warm up to room temperature, whereafter the mixture is boiled for 8 hours under reflux at the boiling point of the mixture. The reaction is monitored by thin layer chromatography (Kiesel gel 60 F 254 on 0.2 mm layer in 9:1 mixture of chloroform and methanol). The solvent is concentrated at reduced pressure (2666 Pa) and the residue is worked up by the method described in Example 4/a.Yield: 4.18 g (82 %), melting point 123-124 OC Analysis C16H18N20 (254.35)
Calculated: C 75.56, H 7.13, N 11.01 95, Found: C 75.41, H 6.99, N 11.12 95.
IR (nujol): 3360 (NH), 3200-3320 (NH2), 1680 (CONH) cm1.
2.54 g base is dissolved in 20 ml ethanol saturated with hydrochloric acid at about 40 OC, and to the solution cooled to room temperature ether is added until crystallization, the mixture is cooled and the precipitated crystalline hydrochloride salt is filtered and dried. Product: 2.56 g (86 %), melting point: 254-256 OC.
Analysis C16H18N20.HCl (290.81)
Calculated: C 66.09, H 6.59, N 9.63, C1 12.19 %,
Found: C 66.12, H 6.67, N 9.72, C1 12.33 95.
Example 6/b.
2,6-dimethyl-r -amino-e -phenyl-acetanilide
2.80 g (0.01 mole) 2,6-dimethyl-α-azido-α-phenyl- acetanilide are added to a suspension of 0.82 9 (0.022 mole) sodium borohydride in 20 ml ethanol cooled to -20 OC. Under stirring the reaction mixture is allowed to warm up to room temperature and the mixture is boiled for 10 hours at the boiling point of the mixture. The reaction mixture is worked up according to Example 5/b. Yield: 4.06 (80 %). Physical constants and the spectral data of the product are identical with the data of the base prepared according to Example 6/a.
Example 6/c.
2,6-dimethyl- oc -amino-Cphenyl-acetanilide 5.04 g (87 %) base is prepared from 5.60 (0.02 mole) 2,6-dimethyl-α-amino-α-phenyl-acetanilide by catalytic hydrogenation according to Example 5/c. The physical constants of the product are the same as the data of the product of Example 6/a.
Example 6/d.
2s6-dimehtyl- 4 -amino- r -phenyl-acetanilide
The product is prepared from 5.60 g (0.02 mole) 2,6 dimethyl-cx-phenyl-cC -acetanilide according to the method disclosed in Example 5/d and the working up of the product is also the same. Yield: 5.20 g (89.6 %). The physical constants and spectral data of the product are identical with those of the hydrochloride salt of Example 6/a.
Claims (4)
1. Process for the preparation of the compounds of the general Formula (I) and salts thereof
- wherein xl stands for azido or amino group,
R stands for hydrogen, C14 alkyl or phenyl which comprises reacting an aniline derivative of the general Formula (II)
- wherein X2 stands for chlorine or bromine,
R stands for hydrogen or C14 alkyl or phenyl with alkali metal azide, and if desired reducing the obtained compound of the general Formula (I) - wherein X1 stands for azido and R is as defined above - prefereably with a complex alkali hydride or by catalytic hydrogenation and converting if desired the obtained product to a salt by reaction with acid.
2. A process as claimed in Claim 1 for the preparation of compound of the general Formula (I) - wherein X1 stands for azido - comprising reacting an aniline derivative of the general Formula (II) - when X2 and R are as given above - with an alkali metal azide in an aqueous solvent or in watermiscible solvent.
3. A process as claimed in Claim 1 in order to prepare compounds of the general Formula (I) - wherein X1 stands for amino, comprising reducing a compound of the general Formula (I) - wherein X1 is azido and R is as given above - with complex alkali hydride in an alcohol solvent by boiling or by catalytic hydrogenation at atmospheric pressure at room temperature.
4. The compounds of formula (I) as defined in claim 1 in which X is an azido group.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU116587A HU199402B (en) | 1987-03-18 | 1987-03-18 | Process for producing alpha-azido- and alpha-aminoacyl anilide derivatives |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8806464D0 GB8806464D0 (en) | 1988-04-20 |
| GB2202535A true GB2202535A (en) | 1988-09-28 |
| GB2202535B GB2202535B (en) | 1991-01-16 |
Family
ID=10953132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8806464A Expired - Fee Related GB2202535B (en) | 1987-03-18 | 1988-03-18 | Amino and azido acyl anilines |
Country Status (3)
| Country | Link |
|---|---|
| FI (1) | FI881250A (en) |
| GB (1) | GB2202535B (en) |
| HU (1) | HU199402B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325485A2 (en) * | 1988-01-22 | 1989-07-26 | Hampshire Chemical Corporation | Preparation of amino acid derivatives |
-
1987
- 1987-03-18 HU HU116587A patent/HU199402B/en unknown
-
1988
- 1988-03-16 FI FI881250A patent/FI881250A/en not_active Application Discontinuation
- 1988-03-18 GB GB8806464A patent/GB2202535B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0325485A2 (en) * | 1988-01-22 | 1989-07-26 | Hampshire Chemical Corporation | Preparation of amino acid derivatives |
| EP0325485A3 (en) * | 1988-01-22 | 1990-09-19 | W.R. Grace & Co.-Conn. (A Connecticut Corp.) | Preparation of amino acid derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| HU199402B (en) | 1990-02-28 |
| FI881250A0 (en) | 1988-03-16 |
| FI881250A (en) | 1988-09-19 |
| GB8806464D0 (en) | 1988-04-20 |
| GB2202535B (en) | 1991-01-16 |
| HUT46295A (en) | 1988-10-28 |
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Effective date: 19940318 |