6-aryl-5-honokalani-2h-1,3-oxazin-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 oxazino 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 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones of General formula

Ar=C6H5R=C6H4Br-p, R'=C6H4OCH3-p (a); Ar=C6H4CH3-p, R=C6H4OCH3-p, R'=C6H4Br-p (b) exhibiting fluorescence properties. It also describes the 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones as a means for marking, copying and recognition using ultraviolet radiation, 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones as additives for reflective paints and method for producing 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones. The technical result obtained new compounds with useful properties. 4 N. and 1 C.p. f-crystals.

The invention from the BU of their receipt, 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.

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.

Available to the applicant sources describe esteem 5-aryl-2,3-dihydro-2,3-furandione with N-benzylideneaniline (L. N. Karpov, N. In.II, S. N. Shurov, Y. S. Andrejchikov. Five-membered 2,3-DIOXOLANYL. XXV. The interaction of 4-unsubstituted and 4-halogen-5-aryl-2,3-dihydro-2,3-furandione with benzylideneamino. // Zhur.org.chem.. 1992. So 28. Vol 4. C. 779-785).

This method is similar taken as a prototype.

(IIIa-p): AG=C6H5, AG’=p-CH3OS6H4, AG=C6H5(b), AG=p-l6H4(in); AG’=p-CH3OS6H4, AG=p-CH3OS6H4: Ah=C6H5(g); p-l6H4(e); AG’=p-NR2WITH6H4, AG=C6H4, Ah=C6H5(W), p-CH3WITH6H4(h), p-l6H4(and); AG’=p-NO2C6H4, Ar’=m-NO2WITH6H4: Ah=C6H5(K), p-CH3OS6H4(l), p-l6H4(m); AG’=C6H5, AG=p-(CH3)2NC6H4: Ah=C6H5(n), p-CH3OS6H4(o), p-l6H4(p)

However, this method is the prototype does not allow to obtain the claimed compounds containing in position 5 oxazinones cycle Hinckley Deputy and with fluorescent svojstvennyh in the literature 6-aryl-5-honokalani-2H-1,3-oxazin-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.

Tasked with developing a method for the synthesis of new substances exhibiting fluorescent properties is carried out by boiling 5-aryl-4-honokalani-2,3-dihydro-2,3-furandione (Ia,b) with N-benzylideneaniline in an inert solvent according to the scheme:

(Ia,b): AG=C6H5(a) AG=C6H4CH3-p (b);

(IIa,b): AG=C6H5R=C6H4VG-p, R’=C6H4OCH3-p (a); AG=C6H4CH3-p, R=C6H4OCH3-p, R’=C6H4r-p (b).

The process is conducted at a temperature 138-140°C, in an inert solvent used is preferably p-xylene or the Dean.

Lowering the temperature of the reaction reduces the yield of the target products to zero due to the fact that the reaction does not go from the reaction mass allocated unreacted educt, raising the temperature of the reaction causes a decrease in the yield of the target product sucena in the field of yellow light when=580-595 nm) upon irradiation with a UV lamp254 nm. Alcohol and chloroform solutions of the compounds (IIA,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 get 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones having similar characteristics with the claimed method, namely, not 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-(3-p-Bromophenyl-2-p-methoxyphenyl-6-phenyl-3,4-dihydro-2H-1,3-oxazin-4-one-5-yl)-3-phenylhydantoin.

A solution of 0.38 g (0.001 mol) of the compound (Ia) and 0.32 g (0.0011 mol) of N-p-methoxy-benzilidene-p-bromoaniline in 5 ml of absolute p-xylene was kept for 20 minutes at 138-140°C, cooled, precipitated precipitate was filtered. Yield 0.49 g (73%). The compound (IIA) C37H26BrN3O3so pl. 252-254°C.

Found, %: C 63.17, H 3.46, N 7. The on-2H-1,3-oxazin-4-one-5-yl)-3-p-trilinolein.

A solution of 0.41 g (0.001 mol) of the compound (IB) and 0.32 g (0.0011 mol) of N-p-brabanthallen-p-anisidine in 5 ml of absolute p-xylene was kept for 20 minutes at 138-140°C, cooled, precipitated precipitate was filtered. Yield 0.53 g (78%). The compound (IIB) C39H30BrN3O3so pl. 210-211°C

Found, %: C 64.11, H 3.42, N 6.65.

Calculated, %: C 63.92, H 3.97, N, 6.90.

Example 3. 2-(3-p-Bromophenyl-2-p-methoxyphenyl-6-phenyl-3,4-dihydro-2H-1,3-oxazin-4-one-5-yl)-3-phenylhydantoin.

A solution of 0.38 g (0.001 mol) of the compound (Ia) and 0.32 g (0.0011 mol) of N-p-methoxy-benzilidene-p-bromoaniline in 5 ml of absolute p-xylene kept for 50 minutes at 130-131°C, cooled, precipitated precipitate was filtered. The output of the compounds (IIA) 0%.

Example 4. 22-(3-p-Bromophenyl-2-p-methoxyphenyl-6-phenyl-3,4-dihydro-2H-1,3-oxazin-4-one-5-yl)-3-phenylhydantoin.

A solution of 0.38 g (0.001 mol) of the compound (Ia) and 0.32 g (0.0011 mol) of N-p-methoxy-benzilidene-p-bromoaniline in a mixture of 5 ml of absolute p-xylene and 5 ml of absolute Dean kept for 10 minutes at 148-150°C, cooled, precipitated precipitate was filtered. The output of the compounds (IIA) 0.25 g (37%), so pl. 252-254°C.

Example 5. 2-(3-p-Bromophenyl-2-p-methoxyphenyl-6-phenyl-3,4-dihydro-2H-1,3-oxazin-4-one-5-yl)-3-phenylhydantoin.

RA is and kept for 20 minutes at 138-140°C was cooled, precipitated precipitate was filtered. The output of the compounds (IIA) 0.49 g (73%), so pl. 252-254°C.

Compounds (IIA, b) - pale yellow crystalline substances, soluble in DMSO, DMF, chloroform, acetic acid, sparingly soluble in acetonitrile, ethyl acetate, insoluble in alkanes and water, not giving a positive test for the presence of the enol hydroxyl with an alcoholic solution of ferric chloride (III). Stable when stored under normal conditions.

In the IR spectra of compounds (IIA, b), taken in vaseline oil, the absorption in the region above 3000 cm-1no, there is a band of stretching vibrations lactam carbonyl group, 1,3-oxazin-4-about the cycle in the field 1650-1675 cm-1.

In the PMR spectra of the compounds (IIA, b), taken in solution in DMSO-d6there are singlets of the protons of methyl groups in the area 2,18-2,36 M. D., singlet protons metoxygroup in the field 3,71-of 3.77 M. D., singlet proton group SN in position 2 1,3-oxazin-4-about the cycle in the field 6,82-7,00 M. D. and the group of signals of aromatic protons in the region 6.82-8,10 M. D.

The proposed method is simple and allows you to get undescribed in the literature 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones in high yields.

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. 6-Aryl-5-honokalani-2H-1,3-oxazin-4-ones of General formula

where AG - C6H5; R6H4VG-p; R'- C6H4OCH3-p (a);

Ar = C6H4CH3-p, R - C6H4OCH3-p;

R' - C6H4VG-p (b)

exhibiting fluorescent properties.

2. 6-Aryl-5-honokalani-2H-1,3-oxazin-4-ones of General formula

where Ar - C6H5; R6H4VG-p; R’ - C6H4OCH3-p (a);

Ar - C6H4CH3-p; R6H4OCH3-p, R’ - C6H4VG-p (b)

as a means for marking, copying and recognition using ultraviolet radiation.

3. 6-Aryl-5-honokalani-2H-1,3-oxazin-4-ones of General fo the; R6H4VG-p; R’ - C6H4OCH3-p (a);

Ar - C6H4CH3-p, R - C6H4OCH3-p, R’ - C6H4VG-p (b)

as additives for reflective paints.

4. The way to obtain 6-aryl-5-honokalani-2H-1,3-oxazin-4-ones of General formula

where Ar - C6H5; R6H4VG-p; R’ - C6H4OCH3-p (a);

Ar - C6H4CH3-p; R6H4OCH3-p, R’ - C6H4VG-p (b)

characterized in that 5-aryl-4-honokalani-2,3-dihydro-2,3-furandione face interaction with N-benzylideneaniline in an inert solvent.

5. The method according to p. 4, wherein the process is conducted at a temperature of 138-140°C.



 

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