JPS6393750A - Novel nitroether derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:Methylene-bis-(2,2-dibromo-2-nitroethyl)ether shown by formula I. USE:Showing strongly germicidal action on bacteria and fungi and useful as a germicide, antiseptic, mildewcide, etc. PREPARATION:A compound shown by formula II is reacted with formaldehyde or paraformaldehyde in the presence of an acidic catalyst to give a compound shown by formula I. The compound of formaldehyde used is preferably 0.3-0.7mol based on 1mol compound shown by formula II. The reaction temperature is 25-150 deg.C, preferably 60-90 deg.C. The starting compound shown by formula II is synthesized by condensing formaldehyde with nitromethane by a caustic alkali and treating the condensate with bromine.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides methylene-bis-(2,2-dibromo-2
- Nitroethyl) ether and Hisono IA production method.

The compound of formula I is a novel compound that has not been described in any literature, exhibits strong bactericidal activity against bacteria and fungi, and is useful as a bactericidal agent, preservative, antifungal agent, and the like.

The compound of formula I can be produced by dehydrating a compound represented by the following formula r No, -C-CH20H (II) with formaldehyde or paraformaldehyde.

The starting material, the compound of formula (1), can be synthesized by condensing formaldehyde and nitromethane with a caustic alkali and then reacting with bromine.

When producing the compound of formula (1), the compound of formula (1) is reacted with formaldehyde or paraformaldehyde in the presence of an acidic catalyst. Formaldehyde is preferably used in a ratio of 0.3 to 0.7 or more per mole of the compound of formula (1).

Examples of the acidic catalyst include polyphosphoric acid, p-)luenesulfonic acid, hydrochloric acid, sulfuric acid, and phosphoric acid. This reaction is preferably carried out in the presence of a solvent. When polyphosphoric acid is used as the acidic catalyst, it can also serve as a solvent. As the solvent, inert solvents such as benzene, toluene, xylene, carbon tetrachloride, ethylene chloride, etc. are used.

The reaction temperature is 25-150°C, preferably 60-90°C, and the reaction is completed in 60 minutes to 3 hours.

The obtained compound of formula I can be isolated and purified by conventional methods.

Compounds of formula I and 2-promo 2- as comparative compounds
The antibacterial spectrum of nitropropanediol-1,3- against various microorganisms is shown in the table below. The values in the table indicate the minimum inhibitory concentration (ppm) determined by the agar dilution method. Also, the symbols B and s in the table.

is Bacillus subtilis, E, c, k'L Engineering'/IJ Shea coli, A, a, Aerobacter aerogenes, P, a, Pseudomonas aeruginosa,
M, p, Micrococcus biogenes tatami var aureus, A, n, Aspergillus niger, P, c
, indicates Penicillium citrinum, T, C0 indicates Trilobosis candida, G, c indicates Geotrichum candidium, and T, T-1, indicates Trichoderma T-1. For the antibacterial activity test, broth agar medium or Czapek agar medium was used; when the former medium was used, the culture conditions were 48 hours at 37°C (Al; when the latter medium was used, the culture conditions were 28
The test was carried out under culture conditions (Bl) for 7 days at °C.

Example 1 2.2-dibromo-2-nitroethanol 5.0 g (0
, 02 mol) and 0.4 g of Hihalaformaldehyde were dispersed in 10.9 g of polyphosphoric acid and heated to 60 to 70°C while stirring.
When heated for 1 hour, the reaction solution turns brown. Next, the reaction solution is cooled to room temperature, and 1Qml of dichloromethane is added to the reaction solution for extraction. The extract is washed twice with 5% sodium bicarbonate solution and twice with water, dried over anhydrous sodium sulfate, and then concentrated using an evaporator to obtain a colorless viscous oil. When a small amount of chloroform is added to this oil to crystallize it and further washed with chloroform, white to slightly yellow crystals of methylene-bis-(2,2-dibromo-2-nitroethyl) ether are obtained with 5.2
9 (yield 51%) is obtained. Melting point 60-61°C.

Elemental analysis value: C3H6N206Br4 = 509.7
4 as CHN Br Calculated value (%) 11.78 1.19 5.49 6
2.70 Actual value (%) 11.94 1.16 5.
39 61.98 NMR analysis: δppm 4.5 (
a n , s >, 4.8 (2H, s ) Example 2 Dissolve 5.0 2-dibromo-2-nitroethanol and heat at 60-70° C. for about 1 hour while stirring. After the reaction is completed, the same procedure as in Example 1 is carried out to obtain 3.5 g (yield: 34%) of methylene-bis-(2,2-sib0%-2-nitroethyl)ether. Elemental analysis values are C: 11°32%, H: 1.06%, N: 5.1
5%, Br: 6500%.

Example 3 2.2-dibromo-2-nitroethanol 5.0, j9
(0.02 mol) and 0.4 g of Hihala formaldehyde were placed in a Yotsuro flask equipped with a dehydration reflux tube, and benzene 2
Disperse in the 0go. Add 0.2 g of p-+-luenesulfonic acid as an acidic catalyst, and heat to reflux with stirring. Approximately 0.351 of water accumulates in the dehydration tube in about 1 hour, and the reaction is completed in about 2 hours. After cooling, the reaction solution is washed several times with 5% sodium bicarbonate solution and water, dehydrated by adding anhydrous sodium sulfate, and concentrated to give a colorless viscous oil. When a small amount of chloroform is added to this oil and left to stand, crystals of methylene-bis-(2,2-dibromo-2-nitroethyl) ether are formed with a yield of 51i<2.
9%) obtained.

Applicant: Permakem Asia Co., Ltd. Agent: Patent attorney Tadashi Kobayashi (1 person)

Claims (1)

[Claims] 1. Methylene-bis-(2,2-dibromo-2) represented by the following formula ▲ Numerical formulas, chemical formulas, tables, etc.
-nitroethyl)ether. 2. Methylene-bis-(2,2-dibromo-2-nitroethyl), which is characterized by dehydrating a compound represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) with formaldehyde or paraformaldehyde. ) How to make ether.