CS267341B1 - 2-Bromomethylphenyl isocyanate and its method of preparation - Google Patents
2-Bromomethylphenyl isocyanate and its method of preparation Download PDFInfo
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Abstract
Riešenie sa týká přípravy novej látky 2-brómmetylfenylizokyanátu vzorca I. Porlstata přípravy spočívá v tom, že na 2- izokyanátotoluén vzorca II sa pósobi N-bromsukcininudoni v prostředí nepolárného organického rozpúšťadla výhodné tetrachlórmetánu alebo benzénu za přítomnosti peroxidických látok ako dibenzoylperoxidu alebo azo-bis-izobutylonitrilu při teplote varu rozpúšťadla.The solution concerns the preparation of a new substance 2-bromomethylphenylisocyanate of formula I. The preparation consists in treating 2-isocyanatotoluene of formula II with N-bromosuccinimidone in a non-polar organic solvent, preferably carbon tetrachloride or benzene, in the presence of peroxidic substances such as dibenzoyl peroxide or azo-bis-isobutylonitrile at the boiling point of the solvent.
Description
Vynález sa týká -2-brómmetylfenylizokyanátu a spňsobu ich přípravy.The invention relates to -2-bromomethylphenyl isocyanate and to a process for their preparation.
Halogénizokyanáty patria k heterokumulénom, kterých bielektrofilné cantrá sa využívajú v organickej syntéze pře přípravu heterocyklických látek. Halogénizokyanáty je možno připravil’ niekolkými sposobmi. Najčastejšie sa pripravujú termickým rozkladom halogénacylazidov v aprotických rozpúšťadlách (P.A.S. Smith : Org. React. 3, 337(1946) ) alebo reakciou příslušných amínov s fosgénom (napr. US Patent 2 480 080 (1945), Monsanto Chemical Co., R.3.Slocombe, E . E. Hardy ).Haloisocyanates belong to heterocumulenes, the white electrophilic cantras of which are used in organic synthesis for the preparation of heterocyclic substances. Halogenated isocyanates can be prepared in several ways. They are most often prepared by thermal decomposition of haloacyl azides in aprotic solvents (PAS Smith: Org. React. 3, 337 (1946)) or by reaction of the corresponding amines with phosgene (e.g. U.S. Patent 2,480,080 (1945), Monsanto Chemical Co., R.3 .Slocombe, E. E. Hardy).
Štúdiom literatúry sa ukázalo, že 2-brómmetylfenylizokyanát nebol doteraz připravený. Predmetom vynálezu je 2-brommetylfenylizokyanát vzorca (I) aCH2BrA study of the literature has shown that 2-bromomethylphenyl isocyanate has not yet been prepared. The present invention provides a 2-bromomethylphenyl isocyanate of formula (I) and CH 2 Br
N=C=O (I) a spňsob jeho přípravy. Podstata sposobu přípravy 2-brómmetylfenylizokyanátu spočívá v tom, že sa na 2-.izokyanátotoluén vzorca (II)N = C = O (I) and method for its preparation. The process for the preparation of 2-bromomethylphenyl isocyanate is based on the fact that the 2-isocyanatotoluene of the formula (II)
(II) poeobi N-brómsukcínimidom v prostředí nepolárného organického rozpúšťadla, výhodné tetrachlórmetánu alebo benzenu za přítomnosti peroxidických látok ako dibenzoylperoxidu za přítomnosti peroxidických látok ako dibenzoylperoxidu alebo azo-bis-izobutyronitrilu pri teplote varu rozpúšťadla.(II) a mixture of N-bromosuccinimide in a non-polar organic solvent, preferably carbon tetrachloride or benzene in the presence of peroxides such as dibenzoyl peroxide in the presence of peroxides such as dibenzoyl peroxide or azo-bis-isobutyronitrile at the boiling point of the solvent.
Výhody sposobu přípravy zlúčeniny I podlá vynálezu spočívají! v tom, že při reakci! nedochádza k adici ! halogenu (t. j. brómu) na skupinu N=C=0.The advantages of the process for the preparation of the compound I according to the invention are! in that in response! there is no addition! halogen (i.e. bromine) to the group N = C = O.
2-Orómmetylfenylizokyanát představuje nový jednoduchý a velmi reaktívny typ bifunkčného syntónu. S amínmi, fenolmi a hydrazímni vystupuje do adično-cyklizačných reakcií prostredníctvam NCO a CI^Br skupin za vzniku šesť a sedemčlenných dusíkatých heterocyklov (napr. benzoxazíny a benztriazepíny). S niektorými nukleoflínými zlúčeninami napr. trifenylfosfínmi poskytuje óniové soli, ktoré je možné využiť pře syntézu derivátov indolu.2-Bromomethylphenyl isocyanate represents a new simple and highly reactive type of bifunctional synthon. With amines, phenols and hydrazimines, it undergoes addition-cyclization reactions via NCO and Cl 2 Br groups to form six and seven membered nitrogen heterocycles (e.g. benzoxazines and benztriazepines). With some nucleophilic compounds, e.g. triphenylphosphines, it provides onium salts which can be used for the synthesis of indole derivatives.
Predmet vynálezu ilustruji! ale neobmedzujú následovně příklady:I illustrate the subject matter of the invention! but do not limit the following examples:
Přikladl .He added.
Zmes 26,6 g (0,2 mól) o-totylizokyanátu, 35,6 g (0,2 mol) N-brómsukcínlmidu a 2,42 g (20 mmol) dibenzoylpero'xidu v 20 ml suchého totrachlórmetánu bola zahríevaná cca 0,5 hodiny do varu pod spatným chladičom. Po ochladem' bol vylúčený sukcínimid odsátý a tetrachlórmetán bol odpařený. Zvyšok bol rozpuštěný v hexéne a odstavený na kryštalizáciu cez noc v chladnlčke při -20 °C.A mixture of 26.6 g (0.2 mol) of o-totyl isocyanate, 35.6 g (0.2 mol) of N-bromosuccinimide and 2.42 g (20 mmol) of dibenzoyl peroxide in 20 ml of dry totrachloromethane was heated to about 0 DEG C. 5 hours to boil under a bad cooler. After cooling, the precipitated succinimide was filtered off with suction and the carbon tetrachloride was evaporated. The residue was dissolved in hexene and allowed to crystallize overnight in a refrigerator at -20 ° C.
Vykrystalizovaný 2-brómmetylfenylizokyanát bol rýchle odsátý. T. t. 0-5 0 C.Výťažok 85 %The crystallized 2-bromomethylphenyl isocyanate was quickly filtered off with suction. M.p. 0-5 0 C. Yield 85%
Příklad 2Example 2
26,6 g (0,2 mól) 2-izokyanáto-toluénu, 35,6 g (0,2 mól) NBS a 2,42 g (20 mmol) dibenzoylperoxidu sa zahrieva v benzéne 0,5 hodiny a spracuje ako v příklade 2. Výťažok 63 %.26.6 g (0.2 mol) of 2-isocyanato-toluene, 35.6 g (0.2 mol) of NBS and 2.42 g (20 mmol) of dibenzoyl peroxide are heated in benzene for 0.5 hour and worked up as in Example 2. Yield 63%.
Získaný 2-brómmety 1feny1izokyanát I je krystalická látka, t.j .· 0-5 °C (z hexánu).The obtained 2-bromomethylphenylisocyanate I is a crystalline substance, i.e. · 0-5 ° C (from hexane).
Sumárny vzorec: CoHzBr NO ϋ OSummary formula: C o H z Br NO ϋ O
Molekulová hmotnost’: 23 2,2Molecular Weight ’: 23 2.2
Elementárna analýza: % C % Η % NElemental analysis:% C% Η% N
Množstvo vypočítané: 45,24 2,82 6,59Amount calculated: 45.24 2.82 6.59
Množstvonájdene: 45,28 2,86 6,54Amount found: 45.28 2.86 6.54
Struktura zlúčeniny I bola dokázaná spektrálnými metodami IC a H NMR.The structure of compound I was proved by IC and 1 H NMR spectral methods.
IČ: V (CHCI., cm1) : 20B0 (N=C=0) *· Π13 X ?IR: V (CHCl 3, cm 1 ): 20B0 (N = C = 0) * · Π13 X?
CS 267341 BlCS 267341 Bl
1H NMR; (COClj, ppm): 4,42 (2H, s, CH2),1 H NMR; (COCl 3, ppm): 4.42 (2H, s, CH 2 ),
7,24 - 7,42 (4H, m, ΗθΓοπ)).7.24 - 7.42 (4H, m, Γθ Γοπ) ).
Spektrálné meraniaSpectral measurements
Infračervené spektrá sa nametali na spektrofotometri SPECORD IR 75(Carl Zeiss Oena). 1H NMR spektrá boli nametané na 80 MHz spektrofotometri Tesla BS 487.Infrared spectra were measured on a SPECORD IR 75 spectrophotometer (Carl Zeiss Oena). 1 H NMR spectra were measured on an 80 MHz Tesla BS 487 spectrophotometer.
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| Application Number | Priority Date | Filing Date | Title |
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| CS881207A CS267341B1 (en) | 1988-02-25 | 1988-02-25 | 2-Bromomethylphenyl isocyanate and its method of preparation |
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| Application Number | Priority Date | Filing Date | Title |
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| CS881207A CS267341B1 (en) | 1988-02-25 | 1988-02-25 | 2-Bromomethylphenyl isocyanate and its method of preparation |
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| CS120788A1 CS120788A1 (en) | 1989-06-13 |
| CS267341B1 true CS267341B1 (en) | 1990-02-12 |
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| CS881207A CS267341B1 (en) | 1988-02-25 | 1988-02-25 | 2-Bromomethylphenyl isocyanate and its method of preparation |
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| CS120788A1 (en) | 1989-06-13 |
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