CS264995B1 - /e/-1-phenyl-2-isocyanato-3-brom-1-propen and process for prrparing thereof - Google Patents
/e/-1-phenyl-2-isocyanato-3-brom-1-propen and process for prrparing thereof Download PDFInfo
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- CS264995B1 CS264995B1 CS881701A CS170188A CS264995B1 CS 264995 B1 CS264995 B1 CS 264995B1 CS 881701 A CS881701 A CS 881701A CS 170188 A CS170188 A CS 170188A CS 264995 B1 CS264995 B1 CS 264995B1
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- CS
- Czechoslovakia
- Prior art keywords
- isocyanato
- phenyl
- propene
- bromo
- formula
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000009835 boiling Methods 0.000 claims abstract description 3
- 150000002978 peroxides Chemical class 0.000 claims abstract description 3
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- -1 (E) -1-phenyl-2-isocyanato-3-bromo-1-propene Chemical compound 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Riešenie sa týká novho /E/-l-fenyl- -2-izokyanáto-3-bróm-l-propénu vzorca I. Jeho příprava spočívá v tom, že na /E/- -l-fenyl-2-izokyanáto-bróm-l-propén vzorca XI sa pósobí N-brómsukcínimidom v prostředí nepolárného organického rozpúšťadla, výhodné tetrachlórmetánu alebo benzénu za přítomnosti peroxidické látky ako dibenzoylperoxidu, alebo azo-bis- -izobutyronitrilu pri teplote varu rozpúšťadla .The solution concerns the new / E / -l-phenyl- 2-isocyanato-3-bromo-1-propene of formula I. His preparation is that on / E / - 1-phenyl-2-isocyanato-bromo-1-propene Formula XI is treated with N-bromosuccinimide in a non-polar organic solvent environment preferably carbon tetrachloride, or benzene in the presence of a peroxide as dibenzoyl peroxide, or azo-bis- -isobutyronitrile at the boiling point of the solvent .
Description
Izokyanáty sú vysokoreaktívne elektrofilné činidlá pomocou ktorých je možné vniesť do molekúl organických látok fragment -HN-CO-. Přítomnost áalšieho reaktívneho centra, v izokyanáte móže byt využitá v následných reakcích pre přípravu heterocyklických zlúčenín. Halogénalkylizokyanáty, ktoré sa pre tento účel často používajú, je možné připravit napr. reakciou halogénalkylamínov s fosgénom alebo rozkladom příslušných acylazidov, ale tiež radikálovou halogenáciou izokyanátov (napr.: DE patent 1 122 058 (1960/1962), Farbf. Bayer; H. Holtschmidt, E. Degener, C. A. 57, 7 113 (1962). Y. G. Balon, V. E Paranyak: Zh. Org. Khim. 12, 522 (1976); ang. 513. R. F. Merrit: J, Org. Chem. 32, 1 633 (1967)).Isocyanates are highly reactive electrophilic agents by means of which the -HN-CO- fragment can be introduced into the organic molecules. The presence of another reactive center in the isocyanate can be utilized in subsequent reactions to prepare heterocyclic compounds. The haloalkyl isocyanates which are frequently used for this purpose can be prepared e.g. by the reaction of haloalkylamines with phosgene or decomposition of the respective acylazides, but also by the radical halogenation of isocyanates (e.g. DE Patent 1 122 058 (1960/1962), Farbf. Bayer; H. Holtschmidt, E. Degener, CA 57, 7 113 (1962)). YG Balon, V. E. Paranyak: Zh., Org. Khim., 12, 522 (1976), ang. 513. RF Merrit: J, Org. Chem., 32, 1633 (1967)).
Štúdiom literatúry sa ukázalo, že (E)-l-fenyl-2-izokyanáto-3-bróm-l-propén nebol doteraz připravený.A literature study has shown that (E) -1-phenyl-2-isocyanato-3-bromo-1-propene has not been prepared to date.
Predmetom vynálezu je (E)-l-fenyl-2-izokyanáto-3-bróm-l-propén vzorca XThe subject of the invention is (E) -1-phenyl-2-isocyanato-3-bromo-1-propene of formula X
N=C=ON = C = O
a spósob jeho pripravy.and the way it was prepared.
Podstata spósobu pripravy (E)-l-fenyl-2-izokyanáto-3-bróm-l-propénu spočívá v tom, že sa na (E)-l-fenyl-2-izokyanáto-l-propén vzorca II ' N-C-0The essence of the process for the preparation of (E) -1-phenyl-2-isocyanato-3-bromo-1-propene consists in reacting (E) -1-phenyl-2-isocyanato-1-propene of formula II 'N-C-O
pósobí N-brómsukcínimidom v prostředí nepolárného organického rozpúšťadla, výhodné tetrachlórmetánu alebo benzénu za přítomnosti peroxidické látky ako dibenzoylperoxidu, alebo azo-bis-izobutyronitrilu pri teplote varu rozpúšťadla.with N-bromosuccinimide in a non-polar organic solvent, preferably carbon tetrachloride or benzene in the presence of a peroxide such as dibenzoyl peroxide or azo-bis-isobutyronitrile at the boiling point of the solvent.
Výhody spósobu pripravy zlúčeniny I podlá vynálezu spočívajú v tom, že pri reakcii nedochádza k adícii brómu na dvojitú vazbu C=C.Advantages of the process for the preparation of the compound I according to the invention are that the reaction does not add bromine to the C = C double bond.
(E)-l-fenyl-2-isokyanáto-3-bróm-l-propén představuje nový, jednoduchý a velmi reaktívny typ bielektrofilu s N=C=O skupinou, ktorý lahko vstupuje s amínmi a hydrazínmi do adično-cyklizačných reakcii za vzniku pat a šesťčlenných heterocyklov (napr. oxazolínov a triazínov).(E) -1-phenyl-2-isocyanato-3-bromo-1-propene is a new, simple and highly reactive type of N = C = O-white electrophile that readily enters addition-cyclization reactions with amines and hydrazines to form and six-membered heterocycles (e.g., oxazoline and triazine).
Predmet vynálezu ilustrujú ale neobmedzujú následovně příklady:The invention is illustrated but not limited by the following examples:
Příklad 1Example 1
Zmes 31,8 g (0,2 mól) (E)-1-feny1-2-izokyanáto-l-propénu, 35,6 g N-brómsukcínimidu a 2,42 g (20 mmol) dibenzoylperoxidu v 20 ml tetrachlórmetánu bola zahrievaná cca 0,5 h do varu pod spátným chladičom. Po ochladení bol vylúčený sukcínimid odsátý a tetrachlórmetán bol odpařený. Zvyšok bol rozpuštěný v hexáne a odstavený na kryštalizáciu v chladničke pri -20 °C.A mixture of (E) -1-phenyl-2-isocyanato-1-propene (31.8 g, 0.2 mol), N-bromosuccinimide (35.6 g) and dibenzoyl peroxide (2.42 g, 20 mmol) in carbon tetrachloride (20 ml) was heated. approx. 0.5 h to reflux. After cooling, the precipitated succinimide was aspirated and the carbon tetrachloride was evaporated. The residue was dissolved in hexane and stored for crystallization in a refrigerator at -20 ° C.
Výťažok 79 až 84 %. T. t. 37 až 39 °C.Yield 79-84%. T. t. Mp 37-39 ° C.
Příklad 2Example 2
Zmes 31,8 g (0,2 mól) (E)-1-feny1-2-izokyanáto-l-propénu, 35,6 g (0,2 mól) N-brómsukcínimidu a 1,64 g (10 mmol) azo-bis-izobutyronitrilu sa zahrieva v benzéne 0,5 h a spracuje ako v příklade 1.A mixture of 31.8 g (0.2 mol) of (E) -1-phenyl-2-isocyanato-1-propene, 35.6 g (0.2 mol) of N-bromosuccinimide and 1.64 g (10 mmol) of azo of bis-isobutyronitrile was heated in benzene 0.5 h and treated as in Example 1.
Výťažok 56 až 63 %.Yield 56-63%.
Získaný (E)-l-fenyl-2-izokyanáto-3-bróm-l-propén I je krystalická látka, t. t. 37 až 39 °C (z hexánu).The obtained (E) -1-phenyl-2-isocyanato-3-bromo-1-propene I is a crystalline solid, m.p. t. Mp 37-39 ° C (from hexane).
Sumárny vzorec: C10HgBrNO Molekulová hmotnost: 237,9Summary formula: C 10 H g BrNO Molecular weight: 237,9
Štruktúra zlúčeniny I bola dokázaná spektrálnými metodami IČ a 1H NMR.The structure of compound I was demonstrated by IR and 1 H NMR spectral methods.
_ -i_ -i
IČ spektrum: V , cm (CHCI.-.) 2 248 (N=C=O) .IR: ν cm (CHCl3) 248248 (N = C = O).
H NMR spektrum: δ, ppm (CDClg) , 4,20 s 2H(CH2), 6,13 s 1H(CH), 7,31 až 7,67 m 5H(H-arom.) .1 H NMR Spectrum: δ, ppm (CDCl 3), 4.20 with 2H (CH 2 ), 6.13 with 1H (CH), 7.31-7.67 m 5H (H-arom.).
Spektrálné meraniaSpectral measurements
Infračervená spektrá sa namerali na spektrofotometri Specord IR 75 (Carl Zeiss Jena). NMR spektrá boli namerané na 80 MHz spektrofotometri Tesla BS 487.Infrared spectra were recorded on a Specord IR 75 spectrophotometer (Carl Zeiss Jena). NMR spectra were recorded on a 80 MHz Tesla BS 487 spectrophotometer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS881701A CS264995B1 (en) | 1988-03-16 | 1988-03-16 | /e/-1-phenyl-2-isocyanato-3-brom-1-propen and process for prrparing thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS881701A CS264995B1 (en) | 1988-03-16 | 1988-03-16 | /e/-1-phenyl-2-isocyanato-3-brom-1-propen and process for prrparing thereof |
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| Publication Number | Publication Date |
|---|---|
| CS170188A1 CS170188A1 (en) | 1988-12-15 |
| CS264995B1 true CS264995B1 (en) | 1989-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS881701A CS264995B1 (en) | 1988-03-16 | 1988-03-16 | /e/-1-phenyl-2-isocyanato-3-brom-1-propen and process for prrparing thereof |
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| Country | Link |
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1988
- 1988-03-16 CS CS881701A patent/CS264995B1/en unknown
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| Publication number | Publication date |
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| CS170188A1 (en) | 1988-12-15 |
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