2-koimeterion-3,4-dihydro-2h-1,3-benzoxazin-4-ones exhibiting fluorescence properties and method of production thereof

 

(57) Abstract:

The invention relates to the field of organic chemistry, namely to new individual compounds of class benzoxazines that exhibit fluorescent properties and can be used as starting products for the synthesis of new heterocyclic systems, as well as substances for sample labeling and additives for reflective paints. Describes 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones of formula I,

where R= H (a), CH3(b) exhibiting fluorescence properties. Also describes 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones as substances for marking, copying and recognition using ultraviolet radiation, 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones as additives for reflective paints and method for producing the above compounds. The technical result obtained new compounds with useful properties. 4 N. and 2 C.p. f-crystals.

The invention relates to the field of organic chemistry, namely to new individual compounds of the class of benzoxazines and method of production thereof, which exhibit fluorescent properties and can be used in the in for sample labeling and additives for reflective paints.

There are various solutions to protect monetary documents, shares, cheques, credit cards, identity cards, passports, using special inks, particularly inks with varying effect, allowing, for example, to move from blue to green depending on the tilt of the document, or paints, which begin to glow only at a certain irradiation, for example, under the action of ultraviolet radiation (see U.S. patent No. 4175776, IPC 42 D 15/00, priority 27.11.78 year). However, the range of these colors at present, small.

Know the use of special paints containing reflecting the substance and, if necessary, aluminum powder (see U.S. patent No. 4066280, IPC 42 D 15/00, priority 03.01.78 year). The disadvantage of applying this paint is the complexity of the drawing on the paper, which leads to restriction of areas of its use relative to the total area of the document.

From literature is known structural analogues of the claimed compounds 2-formylmethylene-4-oxo-3,4-dihydro-2H-1,3-benzoxazines (CHC, 1977, No. 3, S. 322-327).

Structural analogues exhibiting fluorescent properties not identified.

The synthesis is carried out in two stages by slebodnik way it is impossible to obtain 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones, exhibiting fluorescent properties.

The objective of the invention is to develop a simple, one-step retrieval method is not described in the literature 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones, exhibiting fluorescent properties, as well as the expansion of the means, are used as labels to protect documents from unauthorized copying and additives in reflective paint.

The task is carried out by boiling o-gidroksibenziliden arealuxury acids I (a, b) with dicyclohexylcarbodiimide in an inert aprotic solvent according to the scheme:

I, R=H (a), CH3(b); II, R=H (a), CH3(b).

The process is conducted at a temperature of 100-102°C, and in an inert aprotic solvent used 1,4-dioxane.

Compound II (a, b) in the solid state have stable fluorescence (emission in the field of yellow light when =580-595 nm) upon irradiation with UV light of 254 nm. Alcohol and chloroform solutions of compounds II (a, b) have no fluorescence. Fluorescence is retained during storage of the samples under normal conditions for a long time.

From the patent and technical literature were not identified ways to obtain 2-koimeterion-3 original products, solvents in which the reaction takes place, and the temperature, on what basis is it possible to make a conclusion on the compliance of the claimed technical solution the patentability criteria of “novelty” and “inventive step”. The invention is illustrated by the following examples.

Example 1. 2-Penacillin-3,4-dihydro-2H-1,3-benzoxazin-4-one.

A solution of 0.50 g (1,765 mmol) of o-hydroxybenzamide benzoyloxy acid (compound Ia) and 0.36 g (1,765 mmol) dicyclohexylcarbodiimide in 10 ml of absolute dioxane is boiled for 1 hour, cooled, the precipitate of dicyclohexylamine filtered off, the mother liquor is distilled off, the residue is crystallized from benzene. Obtain 0.40 g (85%). Compound Ia. WITH16H11NO3so pl. 198-199°C.

Found, %: C 72,44, N 4,20, N 5,28.

Calculated, %: C 72,45, N 4,18, N 5,28.

Example 2. 2-(4-Methylbenzylamino)-3,4-dihydro-2H-1,3-benzoxazin-4-one.

A solution of 0.52 g (1,765 mmol) of compound IB and 0.36 g (1,765 mmol) dicyclohexylcarbodiimide in 10 ml of absolute dioxane is boiled for 1 hour, cooled, the precipitate of dicyclohexylamine filtered off, the mother liquor is distilled off, the residue is crystallized from benzene. Obtain 0.40 g (82%). Compound IIb. WITH17H13NO3so pl. 185-1B) - pale-yellow crystalline substance, soluble in acetone, chloroform, 1,2-dichloroethane, dimethylsulfoxide, slightly soluble in alkanes, alcohols, insoluble in water. Stable when stored under normal conditions.

In the IR spectra of compounds II (a, b), taken in vaseline oil, there is an absorption band of the lactam carbonyl group benzoxazinones cycle in the field 1700-1705 cm-1and broad absorption band ketone arolina groups involved in the formation of intramolecular hydrogen bonds N-chelate-type region 1630-1640 cm-1.

In the PMR spectra of compounds II (a, b), taken in deuterated chloroform, in addition to the group of signals of aromatic protons in the region 7,21-8,10 memorial plaques are the singlet proton of NH group in the area to 13.29-13,30 M. D., singlet vinyl proton in the field 6,00-6,05 M. D. and singlet proton group SN3when 2,40 M. D. (compound IIB).

The proposed method is simple, one-step and allows you to get not described in the literature 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones with good output.

Optical activity of the proposed compounds can be used individually and in compositions for application is from the encoding.

Mixed with the dyes they can be used for the manufacture of fluorescent paints, glow, which is called the UV and short wavelength visible radiation.

1. 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones of General formula I

where R is H(a), CH3(b)

exhibiting fluorescent properties.

2. 2-Koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones of General formula I as agents for marking, copying and recognition using ultraviolet radiation.

3. 2-Koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones of General formula I as additives for reflective paints.

4. The method of obtaining 2-koimeterion-3,4-dihydro-2H-1,3-benzoxazin-4-ones of General formula

where R is H(a), CH3(b)

characterized in that on-hydroxybenzamide arealuxury acid is subjected to interaction with dicyclohexylcarbodiimide in inert aprotic solvent, followed by separation of the desired products.

5. The method according to p. 4, wherein the process is conducted at a temperature of 100-102°C.

6. The method according to PP.4 and 5, characterized in that as the inert solvent used 1,4-dio is

 

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41 cl, 19 tbl, 193 ex

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