CH326535A - Process for the preparation of dicarboxamides - Google Patents
Process for the preparation of dicarboxamidesInfo
- Publication number
- CH326535A CH326535A CH326535DA CH326535A CH 326535 A CH326535 A CH 326535A CH 326535D A CH326535D A CH 326535DA CH 326535 A CH326535 A CH 326535A
- Authority
- CH
- Switzerland
- Prior art keywords
- phenylene
- amino
- substituted
- dicarboxamides
- naphthylenediamine
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 8
- -1 naphthylene diamine Chemical class 0.000 claims description 8
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SOWPGKJPEXNMCS-UPHRSURJSA-N (z)-2-bromobut-2-enedioic acid Chemical compound OC(=O)\C=C(/Br)C(O)=O SOWPGKJPEXNMCS-UPHRSURJSA-N 0.000 description 1
- ZQHJVIHCDHJVII-UPHRSURJSA-N (z)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(/Cl)C(O)=O ZQHJVIHCDHJVII-UPHRSURJSA-N 0.000 description 1
- LDZSRRMBFGBOAE-UHFFFAOYSA-N 1,4-dichlorobuta-1,3-diene Chemical compound ClC=CC=CCl LDZSRRMBFGBOAE-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- TXXHDPDFNKHHGW-ZPUQHVIOSA-N trans,trans-muconic acid Chemical compound OC(=O)\C=C\C=C\C(O)=O TXXHDPDFNKHHGW-ZPUQHVIOSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
Description
Verfahren zur Herstellung von Dicarbonsäureamiden
Es wurde gefunden, da ssmanwertvolle DicarbonsÏureamide erhÏlt, wenn man 2 Mol 'inesPhenylen-oderNatphthylendiamins,bea. velchem eine Aminogruppe substituiert sein : a. nn, mit : 1. Mol eines gegebenenfalls substituerten DicarbonsÏurehalogenids der Formel y-CO-CH=CH-(CH=CH)n-1-CO-y worin y Chlor oder Brom bedeutet und n die Zahl 1 oder 2 darstellt, umsetzt.
Enthält das erhaltene DicarbonsÏureamid ?ine nicht substituierte Aminogruppe, so kann las DicarbonsÏureamid mit einem Acylessig- ?Ïureester oder mit Keten behandelt, werden.
Als aromatische, gegebenenfalls substitu- @erteDiamine kommen in Betrachtvorzugsweise !-Amino-4-aeetylacetylaminobenzole, welche im Benzolkern beispielsweise durch Halogenatome, Alkylgruppen und Alkoxygruppen wei @ersubstituiert sein k¯nnen, 1-Amino-4-ben : oylacetylaminobenzole, welche an einem oder beiden Benzo) lkernen weitersubstituiert sein k¯nnen, und 1-Amino-4-acetylacetylamino ?aphthaline und 1-Amino-4-benzoylacetylaminonaphthaline, welche ebenfalls noch kerngebundene Substituenten tragen k¯nnen. In al-l, en den genannten Aminen kann die 4 :-stän- dige AcylaeetyMminogrmppedurch,dieAmino- grupp, ersetzt sein.
Dicarbonsäurehalogenide, welche sich. zur Verkn pfung der aromatischen Diamine eignen, sind z. B. die Chloride der FumarsÏure, Chlorfumarsaure, Bromfumarsäure, Mesacon- sÏure, MaleinsÏure, Citracomsäure, Butadien- 1, 4-dicarbonsÏure, 1,4-Dichlorbutadien,-1,4-di earbonsäure und 2-Methylbutadien-1,4-dicar bonsäure.
Die Umsetzung der aromatischen Diamine mit den DicarbonsÏurehalogeniden erfolgt mit Vorteil in wÏsserigem Medium bei einem pH Wert unter 7. Die Gegenwart eines säurebin- denden Mittels beschleunigt die Reaktion. Ge eignete sällrebindende Mittel sind z. B. die Alkalihydroxyde, -carbonate und -acetate, die Erdalkalihydroxyde, -oxyde und -carbonate und N, N-Dimethylaminobenzol.
Die Dicarbonsäurehalogenidle werden den wässerigen Auf schlämmungen oder Losungen der Amine bzw. ihrer Chlorhydrate vorzugsweise in Form von konzentrierten Losungen in organisehen Lö sungsmitteln zugegeben, wobei durch kräftiges Turbinieren der Misehvmg ein stetes Durehein- anderwirbel. der beiden Phasen zu gewährlei- sten ist.
Die neuen DicarbonsÏureamide entspreehen der Zusa. mmensetztmg x-R-NH-CO-CH=CH- (CH=CH)n-1-CO-NH-R-x worin n die oben genannte Bedeutung besitzt, x eine Amino-oder eine substituierte Amino- gruppe und R einen Phenylen- oder Naph-Ï thylenrest., bedeuten.
Sie sind wertvolle Zwischenprodukte und sollen zur Herstellung von Azofarbstoffen Verwenclung finden.
In den nachfolgenden Beispielen bedeuten die Teile Gewiehtsteile, die Prozente Gewichts- prozente, und die Temperaturen sind in Cel ausgraden angegeben.
Beispiel 1
38, 4 Teile l-Amino-4-aeetylacetylaminoben- zol werden in 1200 Teilen Wasser von 60 als Chlorhydrat t gelost. Man kühlt dite lare Losung unter sehr gutem Rühren auf ungefähr 5 ab. Dann lϯt man zu der nun vor- liegenden feinen Suspension innerhalb von 10 Minuten eine Lösung von 70 Teilen kristal- lisiertem Natriumacetat in 140 Teilen Wasser zuflie¯en und beginnt, unmittelbar anschlie ssend, mit dem Zutropfenlässen einer Lösung von 17-19 Teilen Fumarsäurechlorid in 75 Teilen Chlorbenzol. Die Zugabe des Dicarbonsäurechlorids soll gleichmässig erfolgen und mindestens 3 Stunden dauern.
Durch 7usatz von Eis wird die Temperatur der Suspension stets unterhalb von 12 gehalten. Schliesslich rührt man die Masse, ohne sie weiter zu kühlen, über Nacht und filtriert anderntags das vollständig ausgesehiedene hellgelbe Aeylie- rungsprodukt ab. Nach zweimaligem Verrüh- ren des Produites in kalter 1%iger SalzsÏure, Filtrieren und Waschen des Filterrüekstandes mit kaltem Wasser wird das 4, 4'-Diacetylacetylamino-1,1'-fumarsÏurediphenylamid getrocknet. Es liegt in sehr reiner Form vor und ist ein sehwach gelb gefärbtes Pulver, {las bei 345 unter Zersetzung schmilzt.
In der er nachstehenden Tabelle sind weitere DicarbonsÏureamide aufgef hrt, die nach den Angaben des Beispiels l hergestellt werden.
Die Produkte sind gekennzeichnet durch die zu ihrem Aufbau verwendeten aromatisehen Diamine und DicarbonsÏurehalogenide und durch ihren Schmelzpunkt.
Tabelle Beispiel Aromatische Diamine Diearbonsäurehalogenide Sehmelzpunkt 2 2 Mol 1-Aimno-3-methoxy-4-acetyl- 1 Mol FumarsÏurechlorid 273¯ acetylaminobenzol unter Zersetzung
3 2 Mol 1-Amino-3-chlor-4-acetyl- 1 Mol FumarsÏurechlorid 238¯ acetylaminobenzol unter Zersetzung
4 2 Mol 1-Amino-4-benzoylacetyl-1 Mol Pumarsäurechlorid 253 aminobenzol unter Zersetzung
Process for the preparation of dicarboxamides
It has been found that valuable dicarboxamides are obtained if 2 moles of inesphenylene or nataphthylenediamine are used. velchem an amino group may be substituted: a. nn, with: 1. Mol of an optionally substituted DicarbonsÏurehalogenids of the formula y-CO-CH = CH- (CH = CH) n-1-CO-y where y is chlorine or bromine and n is the number 1 or 2, is implemented.
If the dicarboxamide obtained contains an unsubstituted amino group, the dicarboxamide can be treated with an acyl acetic acid ester or with ketene.
Aromatic, optionally substituted @erteDiamines are preferably! -Amino-4-aeetylacetylaminobenzenes, which can be white substituted in the benzene nucleus, for example by halogen atoms, alkyl groups and alkoxy groups, 1-amino-4-ben: oylacetylaminobenzenes, which on one or both benzo) rings can be further substituted, and 1-amino-4-acetylacetylamino-phthalenes and 1-amino-4-benzoylacetylaminonaphthalenes, which can also carry substituents bound in the nucleus. In all of the amines mentioned, the 4: position acylaeetylmino group can be replaced by the amino group.
Dicarboxylic acid halides, which. suitable for linking the aromatic diamines are, for. B. the chlorides of fumaric acid, chlorofumaric acid, bromofumaric acid, mesaconic acid, maleic acid, citracomic acid, butadiene-1, 4-dicarboxylic acid, 1,4-dichlorobutadiene, -1,4-di carboxylic acid and 2-methylbutadiene-1,4-dicar boric acid.
The reaction of the aromatic diamines with the dicarboxylic acid halides is advantageously carried out in an aqueous medium at a pH below 7. The presence of an acid-binding agent accelerates the reaction. Ge suitable sällrebindende agents are z. B. the alkali hydroxides, carbonates and acetates, the alkaline earth hydroxides, oxides and carbonates and N, N-dimethylaminobenzene.
The dicarboxylic acid halides are added to the aqueous slurries or solutions of the amines or their chlorohydrates, preferably in the form of concentrated solutions in organic solvents, a constant vortex being created by vigorous turbination of the mixture. of both phases is to be guaranteed.
The new dicarboxylic acid amides correspond to the assortment. mmensetztmg xR-NH-CO-CH = CH- (CH = CH) n-1-CO-NH-Rx where n has the abovementioned meaning, x an amino or a substituted amino group and R a phenylene or naph -Ï ethylene radical., Mean.
They are valuable intermediate products and should be used for the production of azo dyes.
In the following examples, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius.
example 1
38.4 parts of 1-amino-4-aeetylacetylaminobenzene are dissolved in 1200 parts of 60 water as hydrochloride. The clear solution is cooled to about 5 while stirring very well. Then, within 10 minutes, a solution of 70 parts of crystallized sodium acetate in 140 parts of water is added to the fine suspension that is now present and, immediately afterwards, a solution of 17-19 parts is added dropwise Fumaric acid chloride in 75 parts of chlorobenzene. The addition of the dicarboxylic acid chloride should take place evenly and last at least 3 hours.
The temperature of the suspension is always kept below 12 by adding ice. Finally, the mass is stirred overnight, without cooling it any further, and the next day the completely separated pale yellow fermentation product is filtered off. After stirring the product twice in cold 1% hydrochloric acid, filtering and washing the filter residue with cold water, the 4,4'-diacetylacetylamino-1,1'-fumaric acid diphenylamide is dried. It is in a very pure form and is a faintly yellow colored powder which melts at 345 with decomposition.
The table below lists further dicarboxamides which are prepared according to the information in Example 1.
The products are characterized by the aromatic diamines and dicarboxylic acid halides used for their synthesis and by their melting point.
Table Example Aromatic diamines diacid halides melting point 2 2 mol 1-Aimno-3-methoxy-4-acetyl-1 mol fumaric acid chloride 273¯ acetylaminobenzene with decomposition
3 2 moles of 1-amino-3-chloro-4-acetyl- 1 mole of fumaric acid chloride 238¯ acetylaminobenzene with decomposition
4 2 moles of 1-amino-4-benzoylacetyl-1 mole of pumaric acid chloride 253 aminobenzene with decomposition
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH326535T | 1954-04-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH326535A true CH326535A (en) | 1957-12-31 |
Family
ID=4500269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH326535D CH326535A (en) | 1954-04-29 | 1954-04-29 | Process for the preparation of dicarboxamides |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH326535A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169054A1 (en) * | 2019-02-22 | 2020-08-27 | 浙江海正药业股份有限公司 | CRYSTALLINE FORM OF (E)-α,β-UNSATURED AMIDE COMPOUND, PREPARATION METHOD THEREFOR, AND USE THEREOF |
-
1954
- 1954-04-29 CH CH326535D patent/CH326535A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169054A1 (en) * | 2019-02-22 | 2020-08-27 | 浙江海正药业股份有限公司 | CRYSTALLINE FORM OF (E)-α,β-UNSATURED AMIDE COMPOUND, PREPARATION METHOD THEREFOR, AND USE THEREOF |
| CN111606828A (en) * | 2019-02-22 | 2020-09-01 | 浙江海正药业股份有限公司 | Crystal form of (E)-α,β-unsaturated amide compound and its preparation method and use |
| CN111606828B (en) * | 2019-02-22 | 2023-07-28 | 浙江海正药业股份有限公司 | Crystal form of (E)-α, β-unsaturated amide compound and its preparation method and use |
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