JP2928044B2 - Method for producing bromonitro alcohol compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a bromonitro alcohol compound. More specifically, the present invention relates to a method for producing a bromonitro alcohol compound using tribromonitromethane and nitromethane as starting materials.

[0002]

2. Description of the Related Art Bromonitro alcohols obtained by substituting a bromine atom, a nitro group and a hydroxyl group into a hydrocarbon have bactericidal properties, and in particular, dibromonitro alcohol is known to be useful as an industrial bactericide. Have been.

[0003] Such bromonitro alcohols are usually produced by reacting nitromethane with an aldehyde or ketone in the presence of an alkali, followed by hydroxyalkylation, followed by bromine reaction and bromination. By adjusting the molar ratio of the aldehyde or ketone to be reacted with nitromethane and the bromine molar ratio during bromination, it is said that the corresponding dibromonitro alcohol (see the following scheme) or monobromonitro alcohol can be produced.

[0004]

Embedded image However, in the above reaction 1, various by-products (dihydrogen
Roxymethylnitromethane, trihydroxymethylnit
Methane), and the yield of the desired monohydroxymethyl compound was extremely low at several percent (Berichte d. D. Che.
m. Gesellschaft. 67 , 996-1000 (1964)). Therefore, it was difficult to obtain dibromonitroethanol in good yield even if the reaction product was brominated according to the above-mentioned reaction 2.

Further, the inventors of the present invention, contrary to the above method, first brominated nitromethane to obtain a dibromo compound, and then reacted with an aldehyde to synthesize a desired bromonitro alcohol compound. (Japanese Patent Laid-Open No. 1-132549). However, this method has not been able to sufficiently satisfy the yield of the desired product.

[0006]

Thus, according to the present invention, there is provided tribromonitromethane, nitromethane and the formula (III): R-CHO (III) wherein R represents a hydrogen atom or a lower alkyl group. The aldehyde represented is reacted in the presence of an alkali to give a compound of formula (I) or formula (II):

[0007]

Embedded image (Wherein R is the same as defined above). A process for producing a bromonitroalcohol compound is provided.

In the above formulas (I), (II) and (III), the lower alkyl group represented by R has 1 to 6 carbon atoms.
Is used. Specific examples of the aldehyde of the formula (III) as a raw material include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and the like, with formaldehyde being particularly preferred.

In the method of the present invention, tribromonitromethane, nitromethane and the aldehyde of the formula (III) are reacted in the presence of an alkali, but the method of mixing them is not particularly limited.

However, as a preferred form, it is preferable to add another reaction material in the presence of an alkali in a mixture of tribromonitromethane and any one of the other reaction materials. That is, i) premixing tribromonitromethane and an aldehyde of the formula (III) and adding an alkali thereto, and then adding nitromethane; or ii) premixing tribromonitromethane and nitromethane and adding an alkali thereto. After that, a method of adding an aldehyde of the formula (III) may be mentioned. In the above embodiment, the method i) is particularly excellent in terms of yield. In any case,
These methods are carried out in a single step, that is, by stirring in a system in which the above reaction materials are dissolved or dispersed in a suitable solvent under alkaline conditions. Since this reaction is an exothermic reaction, it is preferable to gradually add the reaction raw materials after the alkali addition.

In the method of the present invention, the compound of the formula (I) or the compound of the formula (II) can be obtained by changing the amount of the reaction raw material to tribromonitromethane as the raw material compound. In order to obtain the compound (3 mol) of the formula (I), it is usual to use an equimolar amount of the aldehyde of the formula (III), that is, 3 mol, with respect to 3 mols of 2 mols of tribromonitromethane and 1 mol of nitromethane. Good. Specifically, about 1 to 1.8 moles of nitromethane and about 3 moles of aldehyde of the formula (III) per 2 moles of tribromonitromethane
５5 mol, more preferably about 1-1.4 mol of nitromethane and about 3-3.8 mol of aldehyde of formula (III) per 2 mol of tribromonitromethane.

To obtain the compound of formula (II) (3 moles)
Usually, 1 mole of tribromonitromethane and 2 moles of nitromethane
It is preferred to use about 2 moles of the aldehyde of the formula (III), that is, about 6 moles per 3 moles in total. Specifically, about 2 to 5 moles of nitromethane and about 6 to 10 moles of the aldehyde of the formula (III) per mole of tribromonitromethane
Moles, more preferably about 2 to 2.6 moles of nitromethane and about 6 to 8 moles of the aldehyde of formula (III) per mole of tribromonitromethane.

In the method of the present invention, it is essential that at least one of the main starting compounds tribromonitromethane and nitromethane be used in an equimolar amount or more. Solvents include polar or non-polar solvents. In particular,
Water, alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, pentamethylene glycol, glycerin, dichloromethane, chloroform, tetrachloromethane , Chloroethane, halogenated hydrocarbons such as dichloroethane, and ethers such as diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, anisole, phenetole, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, and dimethyl ether;
Methylformamide, N, N-dimethylformamide,
Amides such as N, N-diethylformamide, N, N-dimethylacetamide and N-methylpropionamide, and hydrocarbons such as heptane, octane, nonane, decane, dodecane, benzene, toluene and xylene are used. Among them, polar solvents such as water and alcohols are preferable, and water is particularly preferable.

As the alkali used in the method of the present invention, an inorganic alkali compound such as sodium hydroxide,
Examples include hydroxides of alkali metals such as potassium hydroxide and hydroxides of alkaline earth metals such as calcium hydroxide. Of these, sodium hydroxide is particularly preferred.

The alkali used in the reaction is usually preferably dissolved in water and used as an aqueous solution. The concentration of the alkali is arbitrary as long as the reaction is not hindered. For sodium hydroxide, an approximately 10% aqueous solution is usually used.
The amount of the alkali to be added is usually 0.1 to 4 mol based on a catalytic amount, for example, tribromonitromethane.

The reaction temperature is 0 to 50 ° C., preferably 30 ° C.
~ 50 ° C. The reaction time is 5 minutes to 5 hours,
Preferably, it is performed in 1 to 3 hours. The end of the reaction is terminated by exotherm or liquid chromatography (HPLC), N
It can be known by commonly used device analysis means such as MR. In the treatment of the reaction product, stirring is stopped after the addition of water, and the desired product (I) or (II) can be isolated by ordinary means such as liquid separation, extraction, filtration, and distillation. .

Specific examples of the bromonitro alcohol compound (I) or (II) thus obtained include 2,2
2-dibromo-2-nitroethanol, 2-bromo-2-
Nitro-1,3-propanediol, 1,1-dibromo-1-nitro-2-propanol, 3-bromo-3-nitropentane-2,4-diol, 1,1-dibromo-1-nitro-2-
Butanol and the like.

[0018]

【Example】

 Reference Example (Synthesis of Tribromonitromethane) 10 g of water was placed in a three-necked flask equipped with a thermometer and a stirrer.
96 g (0.6 mol) of bromine and 12.2 g of nitromethane
(0.2 mol) was added. Cool the mixture while stirring
And 24 g (0.6 mol) of sodium hydroxide in 50
g while slowly keeping the solution at 20-30 ° C
did. After dropping, stop stirring and separate into two layers.
Was. This lower layer (colorless) is tribromonitromethane
The thing is ¹³Clear from C-NMR, IR, and HPLC analysis
It was easy. Yield is based on theoretical value based on bromine
Percentage. Yield 57g, containing tribromonitromethane
Rate 100%, yield 96%.

Example 1 [Synthesis of 2,2-dibromo-2-nitroethanol] In a three-necked flask equipped with a thermometer and a stirrer, 29.8 g of tribromonitromethane obtained in the above Reference Example (0.
10 mol) and 14 g of a 37% formaldehyde aqueous solution
(0.17 mol) was added. While stirring the mixture, 0.09 g of a 10% aqueous sodium hydroxide solution was added, and then 3.7 g (0.060 mol) of nitromethane was added to 30 to
The solution was added dropwise while maintaining the temperature at 50 ° C. After stirring at 40 ° C. for 1 hour, 10 g of water was added. When the stirring was stopped and the mixture was allowed to stand, two layers were separated. The lower layer (light yellow) was separated, and this was separated into ¹ H-NM
R, ¹³ C-NMR, IR, and HPLC analysis gave the following results. Yields are percentages of theory based on tribromonitromethane. Yield 37.8 g, 2,2-dibromo-2-nitroethanol content 93%, yield 94
%.

Example 2 [Synthesis of 2,2-dibromo-2-nitroethanol] 29.8 g (0.10 mol) of tribromonitromethane obtained in Reference Example in a three-necked flask equipped with a thermometer and a stirrer. And 3.9 g (0.064 mol) of nitromethane. While stirring the mixture, 0.09 g of a 10% aqueous sodium hydroxide solution was added, and 14 g (0.17 mol) of a 37% aqueous formaldehyde solution was added dropwise while maintaining the temperature at 30 to 50 ° C. After stirring at 40 ° C. for 1 hour, water 10 g
Was added. When the stirring was stopped and the mixture was allowed to stand, the mixture was separated into two layers. The lower layer (light yellow) was separated, and this was subjected to ¹ H-NMR, ¹³ C-NM
R, IR, and HPLC analysis gave the following results. Yields are percentages of theory based on tribromomethane. Yield 36.9 g, 2,2-dibromo-2-nitroethanol content 92%, yield 91%.

Example 3 [2-Bromo-2-nitro-1,3-
Synthesis of propanediol) In a three-necked flask equipped with a thermometer and a stirrer, 29.8 g (0.10 g) of the tribromonitromethane obtained in Reference Example.
Mol) and 56 g of a 37% aqueous formaldehyde solution (0.
69 mol) was added. While stirring this mixture, 10
After adding 0.09 g of sodium hydroxide, 13.5 g (0.22 mol) of nitromethane was added dropwise while maintaining the temperature at 30 to 50 ° C. After stirring at 40 ° C. for 1 hour, a pale yellow liquid was obtained. This was analyzed by ¹ H-NMR, ¹³ C-NMR, IR and HPLC, and the following results were obtained. Yields are percentages of theory based on tribromonitromethane. The yield was 99.3 g, the content of 2-bromo-2-nitro-1,3-propanediol was 54.5%, and the yield was 90%. When this solution was cooled in an ice bath, crystals precipitated. The crystals were separated by filtration and washed with a small amount of cold water to obtain white crystals of 2-bromo-2-nitro-1,3-propanediol. Yield 30 g, 2-bromo-2-nitro-1,3-propanediol content 98%.

Comparative Example 1 [Synthesis of 2,2-dibromo-2-nitroethanol] 29.8 g (0.10 mol) of tribromonitromethane obtained in Reference Example in a three-necked flask equipped with a thermometer and a stirrer. And 14 g of a 37% aqueous formaldehyde solution (0.1 g
7 mol) was added. While stirring this mixture, 10%
After adding 0.09 g of an aqueous sodium hydroxide solution and stirring at 40 ° C. for 1 hour, 10 g of water was added. When the stirring was stopped and the mixture was allowed to stand, two layers were separated. Separate the lower layer (light yellow),
LC analysis gave the following results. Yields are percentages of theory based on tribromonitromethane. Yield 3
0.5 g, 2,2-dibromo-2-nitroethanol content 8.1%, tribromonitromethane content 89%, yield 6.6%.

Comparative Example 2 [Synthesis of 2,2-dibromo-2-nitro-ethanol] In a three-necked flask equipped with a thermometer and a stirrer, 61 g (1.0 mol) of nitromethane, 150 g of water, and 81 g of a 31% aqueous solution of formaldehyde were placed. (1.0 mol) was added. The mixture was cooled with stirring and 80 g of sodium hydroxide
(2.0 mol) was dissolved in 240 g of water.
The solution was slowly dropped. After completion of the dropwise addition, stirring was continued for 1 hour, and then 320 g (2 mol) of bromine was added at 0 to + 5 ° C.
While maintaining the temperature. After the addition was completed, 5 g of a 4N-sulfuric acid aqueous solution was added, and after confirming that the reaction solution had become acidic with pH test paper, stirring was stopped, and the mixture was allowed to stand to separate into two layers. The results of quantifying 2,2-dibromo-2-nitroethanol in this lower layer are shown below. Yield 40.2 g, content 41.5%, yield 6.7%

Comparative Example 3 The reaction was carried out in the same manner as in Comparative Example 2 except that 2 mol of formaldehyde was used. The results are shown below. Yield 1.9 g, content 40.0%, yield 0.3%

[0025]

According to the method of the present invention, it is completely different from the conventional method of hydroxyalkylating nitromethane followed by bromination or brominating nitromethane followed by hydroxyalkylation. By using tribromonitromethane having no hydrogen atom involved in alkylation as a main raw material, a target bromonitro alcohol compound is produced in an extremely high yield. The method of the present invention can be said to be a unique method that has never been seen as a chemical method.

Claims (5)

(57) [Claims] 1. A method comprising reacting tribromonitromethane, nitromethane and an aldehyde represented by the formula (III): R-CHO (III) (wherein R represents a hydrogen atom or a lower alkyl group) in the presence of an alkali. , Formula (I) or Formula (II): (Wherein R is the same as defined above). A process for producing a bromonitro alcohol compound, characterized by obtaining a bromonitro alcohol compound represented by the formula: 2. The process according to claim 1, wherein a mixture of tribromonitromethane and an aldehyde of the formula (III) is reacted with nitromethane in the presence of an alkali. 3. The process according to claim 1, wherein a mixture of tribromonitromethane and nitromethane is reacted with an aldehyde of the formula (III) in the presence of an alkali. 4. The method of preparing a compound of formula (I), wherein 2 mol of tribromonitromethane is used in an amount of about 1 to 1.8 nitromethane.
2. The process of claim 1 wherein about 3 to 5 moles of the compound of formula (III) are used. 5. The process according to claim 1, wherein about 2 to 5 moles of nitromethane and about 6 to 10 moles of the compound of formula (III) are used for the preparation of the compound of formula (II) per mole of tribromonitromethane.