SU1004426A1 - Process for producing monomethylcyanine dyes of the 1,3-dimethyl-1,3-dihydropyrimidone-2 series - Google Patents

Description

The invention relates to the preparation of polymethine dyes, in particular, to a new method for the preparation of monometincyanine dyes of the 1,3-dimethyl-1, H dihydropyrimidone-2 series, which are used as spectral sensitizers for halogen-silver emulsions. A known method for producing monometin cyanine dyes, p de 1,3-dimethyl-1, 3-dihydropyrimido on-2 of the formula, Pjd-Q Q "CH-C; 2 IT-R (CK-CH) W. .-:. (1) where Z is the residue of benzthiazole, quinol, 6-methylquinoline, 6-meth oxy-quinoline, pyridine,. 1-methyl-5 chlorobenzimidazole R is methyl, ethyl, -chlorophenyl; p O-1, by reacting 1,3-Dimethyl-A-methyl-1, 3-dihydropyrimidone-2 with a quaternary salt of a heterocyclic base containing an alkyl mercapto group of formula 2 W; R M (U) TCHL-CH) SNZZ where 2, R, n have the indicated meanings; R is methyl, ethyl, in an environment of chlorobenzene under an atmosphere of nitrogen. The yield of the target product is not specified, when playing the method, it is determined that the yield of the target product is 50-61%. The disadvantages of the known method are the necessity of carrying out the reaction at a high temperature in an inert gas atmosphere, the relatively low yield of the target products, the pollution of the environment by toxic and easily volatile alkyl mercaptans resulting from the reaction. The purpose of the invention is to increase the yield / 3 of the target product, simplify the technological process and improve environmental conditions. This goal is achieved by the fact that according to the method for producing monometin cyanine dyes of the 1,3-dimethyl-1,3 dihydropyrimidone-2 series of the general formula (I) by reacting 1,3 dimethyl - + - methylene-1,3 dihydropyrimidone-2 with a quaternary salt of the heterocyclic base in an organic solvent medium with heating followed by isolation of the target product, 1, 3 Dimethyl-4.-methylene-1,3-dihydropyriMon-2 is used as perchlorate as a quaternary salt of a heterocyclic base using a compound of the formula -C Z K-C (CH -CH) 3f where Z, R , n have the indicated values, and the process is carried out in an environment of absolute alcohol of solvency at 70-80 ° C in the presence of triethyls: 1a. Example 1. Obtaining perchlorate 3 methyl-2- (1, 3 -Dimethyl-2-oxo-1, 3 -dihydropyrimidyl- -methine) -benzthiazole (prototype). 6.9 g (0.05 gmol) 1,3-dimethyl-it-methylene-1, 3-dihydropyrimidone-2 and 15.3 g (0.05 g-mol) methyl methyl sulfate-2-methyl mercaptobenzthiazole in 50 ml chlorobenzene is heated for 1 hour at 130 ° C while passing a stream of nitrogen. The precipitate formed is filtered off, washed with carbon tetrachloride, dried, dissolved in 200 ml of water and the dye is isolated as perchlorate. Yield 11.7 g (61 Mp 293-29 C (decomp.). Maximum absorption nm (in alcohol). Found,%: C, 9; H i, 05; N 10,, N ,, OySCE Calculated ,%: C + 6.7; H, 2; Example 2. Preparation of perchlote 3-methyl-2 (1.3 Dimethyl-2-oxo-1., 3 Dihydropyrimidyl-β-methine) -benzthiazoles. To suspension 0, i2 g (0.0005 gmol of perchlorate, 1, 3-dimethyl-β-methylene-1, -dmhydropyrimidone-2 and 0.115 g (0.0005 g-mol) of 3-methyl-2-sulfobenzthiazolium betaine in 1.5 ml of absolute ethyl alcohol, add 0.15 ml of triethylaiine. The reaction mixture is heated for an hour and at 70-80 ° C, cooled, and the precipitated orange crystals are filtered off, washed successively with 1 ml of alcohol and 5 ML-ether. 0.185 g (96%) is obtained, mp 29329 C (decomp.), Absorption maximum kk nm (in alcohol). Example 3. Preparation of 1-ethyl-2- perchlorate 3-dimethyl-2 -OKCo-l, 3 -dihydropyrimidyl-4-methane-quinolini, K suspension 0.12 g (0.0005 g-mol) of perchlorate 1.3 Dimethyl-methylene 1, 3-Dihydropyrimidone -2 and 0, 2 g (0.0005 g-mol) of 1-ethyl-2-sulfohinolinium betaine in 1.5 ml of absolute ethanol were added 0.15 ml of freshly distilled triethylamine. The reaction mixture is heated for 5 hours at. C., cooled, the precipitated crystals are filtered and washed on the filter with 0.5 ml of alcohol and 5 ml of ether. Oto, 17 g (89%) of yellow-orange crystals are obtained. M.p. 198-199 C (from alcohol). Absorption maximum 473 nm (in alcohol), Found,%: Sat 8.6; 8.5 C. Calculated,%; C6 8.61, Example, Preparation of 1-ethyl-2- (1, 3-dimethyl-2-oxo-1, 3-dihydropyrimidyl-β-methine) -6-methylquinolini perchlorate. To a suspension of 0.25 g (0.001 g-mol) of perchlorate, 1, 3-dimethyl-4-methylene-1.3 dihydropyrimidone 2 and 0.25 g (0.001 g-mol) of 1-ethyl 2 sulfo-6- ;. 0.3 ml of triethylamine was added in 3 ml of absolute ethyl alcohol. The reaction mass is heated for 5 hours at 70-80 ° C, cooled, the precipitated crystals are filtered off and washed on the filter with 1 ml of alcohol and 10 ml of ether. 0.31 g (75%) of orange crystals are obtained. M.p. 232-23 + ° C (from alcohol). Absorption maximum 73 nm (in alcohol). Found,%: ce 8.62 ;, 8, Calculated,%: 8.6E. , Example 5. Preparation of perchlorate 1 ethyl-2- (1, 3-dimethyl- -oxo 1 jS DiHydropyrimidyl- + -methine) -6-methoxy-quinolini.

To a suspension of 0.12 g (0.0005 g-mol of perchlorate 1.3 Dimethyl-β-methyl 1, 3-dihydropyrimidone-2 and 0.13 g (0.0005 g-mol) 1-these -2-sulfo-6 0.15 ml of triethylamine was added in 1.5 ml of absolute ethyl alcohol, the reaction mixture was heated for 6 hours at 70-80 ° C, cooled, the precipitate was filtered off, washed on the filter with 0.8 ml of absolute alcohol and 5 ml of ether. 0.16 g (70) of dark orange crystals of T, melting point 193-195 ° C (from alcohol). Maximum absorption 75 nm (in alcohol).

Found: CC 7.62; 7.52

c gHatVe 2НаО

Calculated: Ct 7,71

Example 6. Obtaining perchlorate 1-methyl-2- (1,3 Dimethyl-2-oKco-l, 3 -hydropyrimidyl- -methine) -pyridinium.

To a suspension of 0.12 g (0.0005 g-mol of perchlorate .1,3-D {1 methyl-β-methylene-1, 3-dihydropyrimidone-2 and 0.086 g (0.0005 g mol) of 1-methyl-2- 0.15 ml of triethylamine is added to 1 ml of absolute ethyl alcohol in 1 ml of absolute ethyl alcohol.The reaction mixture is heated for 5 hours at 75-80 ° C, cooled, the precipitated precipitate is filtered off and washed with 0.3 ml of orange crystals on the filter. mp 27227 C (from alcohol). Maximum absorption 67 nm (in alcohol).

Found: With 16.61; sixteen,

.%

Calculated: With 16.67.

Example 8. Obtaining perchlorate 1,3 dimethyl-2- (t3-dimethyl-2-oxo-1, 3 Dihydropyrimidyl- -methine) -5-chlorobenzimidazole,

To a suspension of 0.12 g (0.0005 g-mol of perchlorate 1 W-Dimethyl-methylene-1, 3-dihydropyrimidone-2 and 0.13 g (0.0005 g-mol) 1,3-Dimethyl-2- 0.15 ml of triethylamine is added to 2.5 ml of absolute ethanol in a sulfo-5-chlorobenzimidazolium betaine.The reaction mixture is heated for 5 hours at 7080 ° C, cooled, the precipitate is filtered off and washed on the filter with 0.5 ml of absolute alcohol and 2 ml of ether. 0.15 g (73) of yellow crystals are obtained. Mp 272-273 ° C (from alcohol). Maximum absorption is 364 nm (in alcohol).

Found: se 16.98; 17.04

 4- ° 5 (1 Calculated, I: C 16.99.

The table shows the output monometincyanine dyes of formula (I) according to the proposed method and the prototype.

methane / pyridinium o I.

To a suspension of 0.12 g (0.0005 g-mol) of 1,3-Dimethyl-4-methylene-1, 3-dihydropyrimidone-2 perchlorate and 0.135 g (0.0005 g-mol) of 1- (-chlorophenyl) -4-sulfopyridinium betaine in 1.7 ml of absolute ethyl alcohol was added 0.15 ml of triethylamine. The reaction mixture is heated at 70-80 0 5 h, cooled, the precipitated precipitate is filtered off, the precipitate is washed on the filter with 0.5 ml of absolute alcohol and 3 ml of ether. Obtain 0.19 g (92.5) brilliant

70 79

50

6

92.5

7 8 73

Thus, the proposed method allows to increase the yield of monomethine cyanine dyes of formula (|) by 20-35 compared with the prototype, and to simplify the technological pro7100 (4268.

The process of reducing the temperature of the heterocyclic base salt with a 130–70 ° C to 70–80 ° C and eliminating the inert gas in the organic solution medium and improving the heater when heated, followed by environmental conditions, causes the formation of toxic easily - $ l and due to the fact that, for the purpose of volatile alkyl mercaptans. increase the yield of the target product,

Claims (1)

1.3 Dimethyl-α-methylene-1,3-dihydropyri The method for producing monometincyanino- as a quaternary salt of 1.3 dimethyl dyes, 1,3-cyclic base, uses soy, -dihydropyrimidone-2 of the formula (|) (Iii)  - 15 Z N-R dl lsn; 2 IT-R R- I (SI CH) sy /, where Z, R, n have the specified values of b, where Z is benzthiazole residue, quinoli-a process is carried out in an absolute environment on, 6-methylquinoline, 6-methyl ethyl alcohol at 70-80 ° C in the presence of toxico-quinoline, pyridine, the formation of triethylamine. 1-methyl-5-chlorobenzimidazole; Information sources, R is methyl, ethyl, -chlorophenyl; taken into account in the examination of n 0-1,1. Patent of Germany No. 2057617, the interaction of 1, .3-Dimethyl- -meti. G 03 C 1/485, C 09 B 23/0, flax-1,3 DIHYDROPYrimidone-2 from the Fourth Public 1978 (prototype). simplifying the process and improving environmental conditions 10 midon-2 is used as perchlorate,  -eleven