PL425B1 - The method of obtaining carbamate esters, their alkylated derivatives on nitrogen and carbonic acid esters. - Google Patents

The method of obtaining carbamate esters, their alkylated derivatives on nitrogen and carbonic acid esters. Download PDF

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PL425B1
PL425B1 PL425A PL42520A PL425B1 PL 425 B1 PL425 B1 PL 425B1 PL 425 A PL425 A PL 425A PL 42520 A PL42520 A PL 42520A PL 425 B1 PL425 B1 PL 425B1
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esters
nitrogen
solution
carbonic acid
parts
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PL425A
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Polish (pl)
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Stwierdzono, ze karbaminiany, ich po¬ chodne alkilowane przy azocie i wegla¬ ny fenoli alkilowanych raz jeden w pier¬ scieniu za wyjatkiem krezoli, dzialaja ro- bakopednie. W przeciwienstwie do wol¬ nych fenoli nie draznia one blon sluzo¬ wych i odznaczaja sie brakiem smaku i zapachu. Ich dzialanie trujace jest bardzo nieznaczne i nie wywoluje wplywów po¬ bocznych. Tern wiec odrózniaja sie one przede wszy stkiem od karbaminianów kre¬ zolu i tymolu. W celu ich otrzymania po¬ stepuje sie w ten sposób, ze wolne fenole, lub pochodne, jak np. sole i t. d., w zwykly sposób zamienia sie na weglany lub karba¬ miniany.Przyklad 1. 150 cz. p-butylofenolu o punkcie topli¬ wosci 90° (Beilstein, I. II, str. 765, 2. I) roz¬ puszcza sie w benzolu i do roztworu dodaje sie 80 czesci pirydyny. Potem dolewa sie, przy oziebieniu, 200 cz. 25% benzolowe¬ go roztworu fosgenu. Po pewnym staniu mieszanine gotuje sie przez wiele godzin na lazni wodnej. Ochladza sie i sklóca roz¬ twór z kwasem o temperaturze lodu, przemywa sola kuchenna i po osuszeniu odparowuje roztwór benzolowy. Krysta¬ liczna pozostalosc ponownie rozpuszcza sie w alkoholu, z którego krystalizuje sie ona w iglach o punkcie topi. 108°. Weglan nie posiada ani smaku ani zapachu. W wo¬ dzie jest trudnorozpuszczalny, latwo roz¬ puszcza sie w eterze, chloroformie i ete¬ rze octowym.Przyklad 2.P-butylofenol rozpuszcza sie w takiej ilosci wodnego roztworu lugu sodowego,,jaka akurat jest potrzebna do rozpuszcze¬ nia go i przepuszcza sie przez roztwór fos¬ genu, az do zobojetnienia. Mieszanine po¬ zostawia sie wtedy w spokoju* dopóki wy¬ dzielona masa nie stanie sie krystaliczna, odsysa i krystalizuje ja z alkoholu, i w ten sposób otrzymuje sie, opisany w przykla¬ dzie 1, weglan dwu-p-butylo-fenolu.Przyklad 3. 164 cz. p-izoamylofenolu (1 — 34 — m- butylófenol U]), rozpuszcza sie w ben¬ zolu i dziala na to 121 cz. dwumetyloanili- ny. Te mieszanine dolewa sie powoli do C00 cz. 25% benzolowego roztworu fosge- nu. Po dluzszem stniu sklóca sie kilka¬ krotnie roztwór benzolowy z kwasem sol¬ nym o temperaturze lodu i dolewa plyn mieszajac do roztworu wodnego amon ja¬ ku. Roztwór benzolowy przemywa sie raz jeszcze roztworem soli kuchennej, suszy i odparowuje. Pozostalosc rozpuszcza sie w eterze naftowym. Karbaminjan p-izoa- rnylofenolu jest trudno rozpuszczalny w wodzie, latwo w alkoholu, benzolu i e- terze. Punkt topliwosci lezy przy 73° — 74°.Przyklad 4. 85 cz. p-benzylofenolu i 60 cz. dwume¬ tyloaniliny rozpuszcza sie w benzolu.Roztwór dolewa sie do 300 cz. 25% roz¬ tworu fosgenu w benzolu, po dluzszem sta¬ niu, przerabia go sie, jak wyzej bylo opi-. sane, i na otrzymany chloroweglan dziala sie amonjakiem. Karbaminjan p-benzylo- fenolu po wiekszej czesci wypada z roz¬ tworu benzolowego i moze byc zaraz o- dessany i dla oczyszczenia krystalizuje sie z alkoholu. Z wysuszonego benzolu daje sie jeszcze osiagnac reszta. Punkt topi. karbaminjanu lezy przy 144°.Przyklad 5. 150 cz. p-butylofenolu rozpuszcza sie av benzolu i 121 cz. dwumetyloaniliny, nastepnie dodaje sie pomalu do 600 cz. 25% benzolowego roztworu fosgenu i po¬ zostawia w spokoju. Przeróbka i dzialanie wodnym roztworem odbywa sie jak w przykladzie 3. Z rozcienczonego- alko¬ holu krystalizuje sie ta substancja w blasz¬ kach, z ligroiny w iglach o punkcie topi. 123° do 124°, w alkoholu i benzolu jest la¬ two rozpuszczalna, a w wodzie trudno roz¬ puszczalna.Odpowiedni karbaminjan z p-izopropy- lofenolu ma punkt topi. 93° do 95° i jest la¬ two rozpuszczalny w benzolu, alkoholu i eterze.Przyklad 6. 150 cz. p-butylofenolu rozpuszcza sie w benzolu wraz z 121 cz. dwumetyloanili¬ ny i dodaje pomalu do przesyconego roz¬ tworu benzolowego fosgenu. Mieszanine pozostawia sie w spokoju, nastepnie skló¬ ca z kwasem solnym i na otrzymany chlo¬ roweglan dziala sie 20% roztworem dwu- metyloaminy, a — karbaminjan p-butylo- N — d^metylo-fenylu jest latwo rozpu¬ szczalny w benzolu, eterze i estrze octo¬ wym trudno zas w wodzie. Topi sie przy 92°.Przyklad 7.Do 134 cz. o-allylofenolu dolewa sie 121 cz. dwumetyloaniliny i 200 cz. benzolu i dziala na te mieszanine przesyconym roz¬ tworem benzolowym fosgenu. Otrzymany chloroweglan sklóca sie z rozcienczonym kwasem solnym i razklada amonjakiem.Karbaminjan o-allylofenylowy wykrysta- lizowuje sie z 97% alkoholu, z którego wy¬ pada on w postaci gwiazdzisto polaczo¬ nych igiel o punkcie topi. 122° do 123°.W eterze naftowym jest ten karbaminjan trudnorozpuszczalny, a w benzolu latwiej. PLIt has been found that carbamates, their derivatives alkylated with nitrogen, and carbonates of phenols alkylated once in the ring, except for cresols, act proactively. Unlike free phenols, they do not irritate the mucous membranes and are tasteless and odorless. Their poisoning effect is very slight and produces no side effects. They are therefore distinguished above all by the carbamates of cresol and thymol. In order to obtain them, free phenols or derivatives, such as, for example, salts, etc., are transformed in the usual way into carbonates or carbamates. p-butylphenol having a melting point of 90 ° (Beilstein, I.II, pp. 765, 2.I) is dissolved in benzol and 80 parts of pyridine are added to the solution. Then, while cooling, 200 parts are added. 25% benzene phosgene solution. After standing, the mixture is boiled for many hours in a water bath. The solution is cooled and mixed with an acid at ice temperature, washed with common salt and, after drying, the benzole solution is evaporated. The crystalline residue is redissolved in the alcohol from which it crystallizes in melting point needles. 108 °. Weglan has neither taste nor smell. It is hardly soluble in water, easily dissolved in ether, chloroform and acetic ether. Example 2 β-Butylphenol is dissolved in the amount of aqueous sodium liquor just needed to dissolve it and passed through through the phosgene solution until it is neutral. The mixture is then left undisturbed until the separated mass becomes crystalline, suction filtered and crystallized from alcohol, and thus the di-p-butyl-phenol carbonate described in Example 1 is obtained. 164 part p-isoamylphenol (1-34 - m-butylphenol U]), is dissolved in petrol and is affected by 121 parts. dimethylanilines. This mixture is slowly poured to C00 parts. 25% benzene phosgene solution. After a longer period of time, the benzole solution is mixed with hydrochloric acid at ice temperature several times and the liquid is added to the aqueous ammonium solution by stirring. The benzole solution is washed once more with common salt solution, dried and evaporated. The residue is dissolved in petroleum ether. P-isornylphenol carbamate is sparingly soluble in water, easily in alcohol, benzene and ether. The melting point is at 73 ° - 74 °. Example 4. 85 parts p-benzylphenol and 60 parts Dimethylaniline is dissolved in benzene. The solution is poured to 300 parts. A 25% solution of phosgene in benzol, after prolonged standing, is processed as described above. sane, and the resulting chlorinated carbonate acts as an ammonia. The p-benzylphenol carbamate for the most part falls out of the benzol solution and can be immediately sucked off and crystallizes from the alcohol for purification. The rest can still be achieved from dried benzol. The point melts. carbamate is at 144 °. Example 5 150 parts. p-butylphenol is dissolved in benzol and 121 parts. dimethylaniline, then slowly added to 600 parts. 25% benzol phosgene solution and left alone. Working up and treatment with the aqueous solution is as in Example 3. This substance is crystallized from the diluted alcohol in the lamellae, from ligroin in the melting point needles. 123 ° to 124 °, it is slightly soluble in alcohol and benzol and sparingly soluble in water. The corresponding carbamate of p-isopropylphenol has a melting point. 93 ° to 95 ° and is easily soluble in benzol, alcohol and ether. p-butylphenol dissolves in benzol along with 121 parts of dimethylaniline and add pomal to a supersaturated solution of benzole phosgene. The mixture is left undisturbed, then mixed with hydrochloric acid and the obtained chlorocarbonate is treated with a 20% solution of dimethylamine, and p-butyl-N-d-methyl-phenyl carbamate is easily dissolved in benzene, ether and acetic ester can hardly be found in water. Melts at 92 °. Example 7 to 134 parts o-allylphenol is added 121 parts. dimethylaniline and 200 parts benzol and treat the mixture with a supersaturated benzene solution of phosgene. The resulting chlorocarbonate is mixed with dilute hydrochloric acid and is broken down into ammonia. The o-allylphenyl carbamate is crystallized from 97% of the alcohol, from which it falls out in the form of star-connected needles with a melting point. 122 ° to 123 °. This carbamate is hardly soluble in petroleum ether and easier in benzol. PL

Claims (1)

1. Zastrzezenie patentowe. Sposób otrzymywania estrów karbami- nowych, ich pochodnych alkilowanych przy< azocie i estrów kwasu weglowego, tern znamienny, ze raz alkilowane tv pier¬ scieniu fenole, za wyjatkiem krezoli, lub ich pochodne przeprowadza sie w zwykly sposób w weglany lub w karbaminiany; Farbenfabriken vorm. Friedr. Bayer & Co. Zastepca: Cz. Raczynski, rzecznik patentowy. ZAKLGRAF.KOZIANSKICH W WARSZAWIE PL1. Patent claim. A method for the preparation of carbamate esters, their nitrogen-alkylated derivatives and carbonic acid esters, characterized by the fact that once alkylated in the ring, phenols, except for cresols, or their derivatives, are converted into carbonate or carbamates in the usual manner; Farbenfabriken vorm. Friedr. Bayer & Co. Deputy: Vol. Raczynski, patent attorney. KOZIANSKI ZLGRAFES IN WARSAW PL
PL425A 1920-07-01 The method of obtaining carbamate esters, their alkylated derivatives on nitrogen and carbonic acid esters. PL425B1 (en)

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