Ueber die Einwirkung von Sulfurylchlorid auf Urethan

Abstract

Met h y l-a t h y 1-pt o ly 1p h e n a c y 1-am m on i urn b r o ni i d, (CH,) (cz Hb)(CHs. Cg H,) (CH:,. G o. C6H5)N.Br. Molekulare Mengen Methyl-athyl-p-toluidin und w-Bromacetophenon werden bis zur Liisung des Letzteren gelinde erwarmt. Nach 4 Stunden ist die Mischung zu einer amorphen, durchsichtigeri Masse erstarrt. Durch Krystallisation aus Alkohol-Aether erhalt man indesserr schone, farblose und luftbestandige Nadeln, die bei 116-1 1 T O schmelzen, ohne eine Umwandlung zu erleiden. 0.1493 g Sbst.: 5.6 ccm N (19, 746mm). C1~HzzOh'Br. Ber. N 4.02. Gef. N 4.31. 116. F r i t z Ephraim: Ueber die Einwirkung von Sulfurylchlorid auf Urethsn. (Eingegangen am 30. Januar 190;'). Rei der Einwirkung von Sulfurylchlorid auf Ammoniak entsteht bekauntlich') u. a. das Sulfamid, SOz(NHa)a, doch ist die Ausbeute an r e i n e m Sulfamid uach H a n t s c h und Holla) ausserordentlich gering (I pCt. des angewandten Sulfurylchlorids). D a nun Sulfurylchlorid auf aliphatische Amine ziemlich g l a t t unter Bildung der organischen Sulfamidderivate reagirt, so wurde versucht, aus Urethan und Sulfur) lchlorid zuui Sulfourethan, SOz(NH. COz Cz Hs)~, zu ge

Esters of Carbamic Acid

“…Reagents which react as indicated in the above equation are sulfuryl chloride (LXIIa, (A) = S02) (96, 120) and phosgene (LXIIb + LXIII, (A) = CO) (9,133,256). These reagents afford only allophanates in the absence of base (120,211).…”

Allophanates.

“…In 1886 Loeb (139) first reported that phosgene would react with ethyl carbamate to give an allophanate. Ethyl allophanate Later, thionyl chloride (68,163,187,218,224), sulfuryl chloride (60), and phosphorus pentoxide (14) were found capable of carrying out the conversion. Ethyl allophanate and triacylamides are ammonolyzed to the allophanate (52,54), N(COOR)3 + NH3 -*• ROCONHCONHí + ROCONH2 + ROH while dicarbethoxy cyanamide may be selectively hydrolyzed to give, in one case, an allophanate (53).…”

“…Rovira (171) found that potassium benzylate could be used to decompose and analyze the allophanates, since it led to the quantitative evolution of ammonia, which may be absorbed in standard sulfuric acid and titrated. Cold alkalies decompose the allophanates also, but only slowly, so that it is possible to reprecipitate the allophanates from the alkaline solutions if the solutions are neutralized promptly (60,143). Baeyer (4) reported that with potassium hydroxide, potassium carbonate formed and no potassium allophanate was obtained.…”

“…Salts of allophanates have been prepared by the reaction of bases with ethyl allophanate (18,60,130,176,208). In this way, the barium (130,176), calcium (130), potassium (130,143), and sodium (60, 130) salts have been prepared.…”

“…It is not entirely surprising that treatment of the barium salt with neutral silver oxide or lead acetate failed to precipitate the new metal salt (130). It is interesting to note that a disodium salt of allophanic acid has been isolated by treating ethyl carbamate with sodium in benzene (60).…”