DE667845C - Process for the preparation of symmetrical dioxalkylated aminoarsenobenzenes - Google Patents
Process for the preparation of symmetrical dioxalkylated aminoarsenobenzenesInfo
- Publication number
- DE667845C DE667845C DEI56681D DEI0056681D DE667845C DE 667845 C DE667845 C DE 667845C DE I56681 D DEI56681 D DE I56681D DE I0056681 D DEI0056681 D DE I0056681D DE 667845 C DE667845 C DE 667845C
- Authority
- DE
- Germany
- Prior art keywords
- symmetrical
- ether
- aminoarsenobenzenes
- amino
- water
- 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
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- AWYSLGMLVOSVIS-UHFFFAOYSA-N phenyl(phenylarsanylidene)arsane Chemical compound C1=CC=CC=C1[As]=[As]C1=CC=CC=C1 AWYSLGMLVOSVIS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001023 sodium amalgam Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 description 2
- CXKRDMQZBMZKKJ-UHFFFAOYSA-N arsine oxide Chemical class [AsH3]=O CXKRDMQZBMZKKJ-UHFFFAOYSA-N 0.000 description 2
- VJWWIRSVNSXUAC-UHFFFAOYSA-N arsinic acid Chemical class O[AsH2]=O VJWWIRSVNSXUAC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- -1 amino arsenic benzenes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 238000010254 subcutaneous injection Methods 0.000 description 1
- 239000007929 subcutaneous injection Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/66—Arsenic compounds
- C07F9/70—Organo-arsenic compounds
- C07F9/74—Aromatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
Verfahren zur Herstellung von symmetrischen dioxalkylierten Aminoarsenobenzolen Es. ist bekannt, d@aß primäre Aminobenzolarsins.äuren, die noch andere Substituenten im Benzolkernenthalten können, bei der Reduktion in symmetrische Aminoarsenbenzole übergehen, die in Form der freien Base in Wasser unlöslich sind.Process for the preparation of symmetrical dioxalkylated aminoarsenobenzenes It. it is known that primary aminobenzolar acids have other substituents can contain in the benzene nucleus, in the reduction to symmetrical amino arsenic benzenes pass over, which are insoluble in water in the form of the free base.
Es wurde nun gefunden, daß man durch Einführung von zwei gleichen oder verschiedenen Oxyalkylresten in die Aminogruppe von Aminobenzolarshi,s;äuren und nachträgliche Reduktion dieser Säuren, z. B. mittels unterphosphorig.er Säure oder Natriumhydrosulfi.t, zu symmetrischen dioxyalkylierten Aminoarsenobenzolen gelangt, die sich. auch in Form der freien Base in Wasser sehr leicht lösen. Ebenso kann man zunächst die Arsins.äuren in die entsprechenden Arsenoxyde überführen und diese dann in essigsaurer Lö,-sun:g mittels NTatriumamalgam zu den freien Arsenobenzolen reduzieren. Ferner entsteht auch durch Einwirkung eines Arsenoxydes auf das zugehörige Arsin in wäßriger Lösung unmittelbar das freie symmetrische Arsenobenzol.It has now been found that by introducing two identical or various oxyalkyl radicals into the amino group of aminobenzolar acids and subsequent reduction of these acids, e.g. B. by means of unterphosphorig.er acid or Natriumhydrosulfi.t, to symmetrical dioxyalkylated Aminoarsenobenzenes gets that down. also dissolve very easily in water in the form of the free base. as well one can first convert the arsinsic acids into the corresponding arsenic oxides and this then in acetic acid solution using N sodium amalgam to the free arsenobenzenes to reduce. Furthermore, arsenic oxide affects the associated substance Arsine in aqueous solution directly forms the free symmetrical arsenobenzene.
Durch die vorherige Einführung der beiden gleichen oder verschiedenen Oxyalkylreste in die primären Arsinsäuren, die in bekannter Weise durch Umsetzung mit Alkylenoxyden erfolgt, ist die Stellung der einzelnen Oxyalkylreste auch in den daraus durch Reduktion gewonnenen dioxyalkylierten Aminoarsic#nobenzolen genau bestimmt.By previously introducing the two same or different Oxyalkyl in the primary arsinic acids, which in a known manner by reaction takes place with alkylene oxides, the position of the individual oxyalkyl radicals is also in the dioxyalkylated Aminoarsic # nobenzolen obtained therefrom by reduction certainly.
Diese Verbindungen zeichnen sich durch große Ungiftvgkeit aus und
zeigen im Gegensatz zu den monoal'kylierten bzw. nicht oxyalkylierten Aminoarsenobe,nzolen,
die nur in Form der Salze oder der Forrnald,ehydsulfoxylat- oder -bisulfitderivate
wasserlöslich sind, bei der .subkutanen Injektion nur sehr geringe Reizwirkung.
Dieselbe Verbindung wird erhalten, wenn man 38,1 g 3-(Bis,dioxypropyl )-amino-4-oxybenzol-l-arsins.äure in 38 ccm Wasser löst und mit r 2o ,g Natriumhydrosulfit etwa. 1!2 Stunde auf 65 bis 7o° erwärmt. Nach dem Absaugen der anorganischen Salze sch:ei- abgesaugt und mit Äther gewaschen. Das gelbe Pulver ist sehr leicht in Wasser löslich, aber unlöslich in Äthylalkohol, Äther und Aceton.The same compound is obtained when 38.1 g of 3- (bis, dioxypropyl) -amino-4-oxybenzene-l-arsinic acid are dissolved in 38 cc of water and about 20 g of sodium hydrosulfite are added. Heated for 1 1/2 hours to 65 to 70 °. After suctioning off the inorganic salts: sucked off and washed with ether. The yellow powder is very easily soluble in water, but insoluble in ethyl alcohol, ether and acetone.
3. 67,5 g 3, 3'-Bis-(dioxypropyloxyäthyl)-amino - 4, 4'- dioxyarsenobenzoldichlorhydrat, dargestellt nach Patent 649 409 (Beispiel 3), aus, der abgesaugt, mit Äther gewaschen und getrocknet wird. Die Verbindung ist unlöslich in Äthylalkohol und Äther, leicht löslich in Wasser. saure Lösung wird durch Zugabe von Natriumcarbonat lackmusneutral gemacht und die klare gelbe Flüssigkeit in Äthylalkohol eingerührt. Hierbei fällt 3, 3'-Di-(bisdioxypropyl)-,ämino-4, 4'-dioxyars,enobenzol det sich ,aus dem gelben Filtrat auf Zusatz von Aceton 3, 3'-Di-(bisdioxypropyl)-amino-4, 4'-dioxyars@enobenzol ,als gelber Nieder-:D aus, der abgesawgt und mit Aceton gewaschen wird.3. 67.5 g of 3,3'-bis (dioxypropyloxyethyl) -amino - 4,4'-dioxyarsenobenzene dichlorohydrate, shown according to patent 649 409 (Example 3), which is suctioned off, washed with ether and dried. The compound is insoluble in ethyl alcohol and ether, easily soluble in water. acidic solution is made litmus neutral by adding sodium carbonate and the clear yellow liquid is stirred into ethyl alcohol. Here, 3, 3'-di- (bisdioxypropyl) -, aemino-4, 4'-dioxyars, enobenzene det, from the yellow filtrate on the addition of acetone 3, 3'-di- (bisdioxypropyl) -amino-4, 4'-dioxyars @ enobenzene, as a yellow low: D from, which is sawed off and washed with acetone.
2. Die Lösung, von 61, 5 g 3, 3'-Dioxy-4, 4'-'ch" - (bis:oxyäthyl) -a;minoarsenob-enzoldi% chlorhydrat, hergestellt nach Patent 646409 (Beispie12), wird nach den Neutralisieren mittels Natriumcarbonat in Äthylalkohol eingerührt und das .ausgeschiedene 3, 3'-D@ioxy-4, 4'-di-(bisoxyäthyl)-aminoarsenobenzol werden wie bei den anderen Beispielen in wäßriger Lösung mittels Natriumcarbonat neutralisiert. Aus dieser Lösung fällt auf Zusatz von Äthylalkohol und Äther ein hellgelher Niederschlag von 3, 3'-Bis-(dioxypropyloxyäthyl)-amino-4, 4'-dioxyarsenobenzol 4. Aus der wäßrigen Lösung von 84,9g 3, 3'-Di-(bisdioxypropyl)-amino-4, 4'-dioxy-5, 5'-di - (acetylamino) - arsenobenzoldichlorhydrat, hergestellt nach Patent 667 844 (Beispiel scheidet sich nach dem Neutralisieren mittels Natriumcarbonat auf Zugabe eines Gemisches von Äthylalkohol und Äther ein gelber, aus, der abgesaugt, mit Äther gewaschen und zur völligen Reinigung nochmals in Wasser gelöst und wiederum mittels Äthylalkohol und Äther gefällt wird. Die Verbindung ist ebenfalls sehr licht wasserlöslich, aber in Äthylalkohol und Äther unlöslich.2. The solution of 61.5 g of 3, 3'-dioxy-4, 4 '-' ch "- (bis: oxyethyl) -a; minoarsenob-enzoldi% chlorohydrate, prepared according to patent 646409 (Beispie12), is according to the neutralization with sodium carbonate is stirred into ethyl alcohol and the precipitated 3,3'-D @ ioxy-4,4'-di- (bisoxyethyl) -aminoarsenobenzene are neutralized as in the other examples in aqueous solution with sodium carbonate Addition of ethyl alcohol and ether a light gelher precipitate of 3,3'-bis- (dioxypropyloxyethyl) -amino-4, 4'-dioxyarsenobenzene 4. From the aqueous solution of 84.9g of 3,3'-di- (bisdioxypropyl) -amino -4, 4'-dioxy-5, 5'-di - (acetylamino) - arsenobenzene dichlorohydrate, produced according to patent 667 844 (example separates after neutralization with sodium carbonate on addition of a mixture of ethyl alcohol and ether a yellow, which is sucked off, washed with ether and dissolved again in water for complete purification and again precipitated with ethyl alcohol and ether. The compound is also very lightly water-soluble, but insoluble in ethyl alcohol and ether.
Dieselbe Verbindung wird erhalten, wenn man zu:n,äcbs: 3-(Bisdioxypropyl)-ainino-4-oxybenzol- 5 -acetylamino-i-arsinsäure entsprechend Patent 638 265 (Beispiel i), mittels s,chwefli;ger Säure und Jodkali in 3-(Bisdioxypropyl) -amino-4-oxyb enzol- 5-,acetylamino- i -arsinoxyd überführt und 19,5;g dieses Arsinoxydes in essigsaurer Lösung portionsweise mit 85- 4.% Natriumamalgam versetzt. Sobald alles Natriumamalgam verbraucht ist, wird vom Quecksilber abdekantiert, die klare Flüssigkeit in die zehnfache Menge Methylalkohol eingerührt, von den ausgeschiedenen anorganischen Salzen abfiltriert und dass gelbe Filtrat mit Äther gefällt. Hierbei scheidest sich 3, 3'-Di-(bisdioxypropyl)-amino-4, 4'-dioxy-5, 5'-di-(acetylamino)-arsenobenzol als gelpulveriger Niederschlag von 3, 3'-Di-(bisdioxypropyl) -amino - 4, 4'-dioxy-5, 5'-ch-(acetytamino) -arsenobenzol ber Niederschlag aus, der abgesaugt und mit Äther gewaschen wird. Löst man ferner 19,5 g obigen Arsinoxydes und I8,3 g des entsprechenden Arsins, das in üblicher Weise durch Reduktion der Arsinsäure mittels Zinkstaub und Salzsäure erhalten wird, in 5o ccm Wasser, so färbt sich die Flüssigkeit unter Erwärmen dunkelgelb, und es scheidet sich hieraus beim Einrühren in ein Gemisch von Äthylalkohol und Äther ein gelber Niederschlag von 3, 3'-Di-(bisdioxyp-ropyl)-Amino-4, 4'-dioxy-5, 5'-di-(acetylamino)-arsenobenzol aus.The same compound is obtained when adding: 3- (bisdioxypropyl) -ainino-4-oxybenzene-5-acetylamino-i-arsinic acid according to Patent 638 265 (Example i), by means of sulphurous acid and potassium iodide in 3- (bisdioxypropyl) -amino-4-oxybenzene- 5-, acetylamino- i -arsine oxide and 19.5 g of this arsine oxide in acetic acid solution was added in portions with 85-4 % sodium amalgam. As soon as all the sodium amalgam has been consumed, the mercury is decanted off, the clear liquid is stirred into ten times the amount of methyl alcohol, the inorganic salts which have separated out are filtered off and the yellow filtrate is precipitated with ether. This separates 3,3'-di- (bisdioxypropyl) -amino-4, 4'-dioxy-5, 5'-di- (acetylamino) arsenobenzene as a gel-powdery precipitate of 3,3'-di- (bisdioxypropyl) - amino - 4, 4'-dioxy-5, 5'-ch- (acetytamino) -arsenobenzene from precipitate, which is filtered off with suction and washed with ether. If 19.5 g of the above arsine oxide and 18.3 g of the corresponding arsine, which is obtained in the usual way by reducing arsinic acid with zinc dust and hydrochloric acid, are also dissolved in 50 cc of water, the liquid turns dark yellow when heated and it separates when stirred into a mixture of ethyl alcohol and ether, a yellow precipitate of 3,3'-di- (bisdioxyp-ropyl) -amino-4, 4'-dioxy-5, 5'-di- (acetylamino) arsenobenzene results .
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI56681D DE667845C (en) | 1936-12-19 | 1936-12-20 | Process for the preparation of symmetrical dioxalkylated aminoarsenobenzenes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE216823X | 1936-12-19 | ||
| DEI56681D DE667845C (en) | 1936-12-19 | 1936-12-20 | Process for the preparation of symmetrical dioxalkylated aminoarsenobenzenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE667845C true DE667845C (en) | 1938-11-21 |
Family
ID=25762326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI56681D Expired DE667845C (en) | 1936-12-19 | 1936-12-20 | Process for the preparation of symmetrical dioxalkylated aminoarsenobenzenes |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE667845C (en) |
-
1936
- 1936-12-20 DE DEI56681D patent/DE667845C/en not_active Expired
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