CN102311361B - A compound of N- nitro-2,4,6-trifluoroaniline, synthesis method and application thereof - Google Patents

Abstract

The present invention discloses a compound of N-nitro-2,4,6-trifluoroaniline. The invention further discloses a synthesis method for the compound. The method comprises that: 2,4,6-trifluoroaniline is adopted as a raw material; the 2,4,6-trifluoroaniline reacts with nitric acid to generate 2,4,6-trifluoroaniline nitrate; the 2,4,6-trifluoroaniline nitrate and acetic anhydride are subjected to a dehydration reaction; the resulting reaction solution is subjected to alkaline washing and acid precipitation to obtain the N-nitro-2,4,6-trifluoroaniline. The invention further discloses an application of the compound as an active ingredient of a plant growth regulator. The compound provided by the present invention provides a more significant plant growth regulation effect than N-nitro-2,4,6-trichloroaniline and N-nitro-2,4,6-tribromaniline, and provides the high selectivity for the growth regulation of the rice root.

Description

Compound N-nitro-2,4,6-trifluoromethyl aniline and synthetic method thereof and application

Technical field

The present invention relates to compound N-nitro-2,4,6-trifluoromethyl aniline, the invention still further relates to the synthetic method of this compound and in the application as in plant-growth regulator effective ingredient.

Background technology

Barring Cross, Prithvi R.Bhalla etc. has reported N-nitro-2 in patent US4643755,4,6-trisubstituted benzene aminated compounds has and suppresses to extend, promote sturdy effect the stem of plant, and emphasis has been reported N-nitro-2,4,6-bromamide is active to the dwarfing of the wheat of different growth phases, paddy rice and healthy and strong adjusting.Thomas D.O ' Neal etc. has reported that in patent US4367339 N-nitro substituted aniline compounds and inorganic salt thereof, organic salt promote ornamental plant Blooming, the plant growth regulating activity that the crops such as inducing paddy rice, wheat tiller and increase production.

At home, the Xie Jiugao of Hua Zhong Agriculture University taught N-nitro-2 that began one's study in 1986, and 4,6-trichloroaniline compounds filtered out active significant economic benefits and social benefits element-II (PGR) (CN1125509) in 1992.This compounds has strong physiological regulatory action to monocot crops.For example, promote rice seed germination, strengthen seedling quality, strengthen and tiller, increase effective fringe and setting percentage, volume increase etc., hard grass, amur foxtail, barnyard grass are had to certain restraining effect.

N-nitro substituted aniline compounds in aforementioned many pieces of patents, report there is antibacterial, weeding, the biological activity such as plant growth regulating.When the substituted element in molecule on phenyl ring is halogen, the biological activity of molecule is relatively better, on phenyl ring, has successfully introduced three bromine atoms and three chlorine atoms for 2,4,6, but fail to introduce three fluorine atoms simultaneously, obtains N-nitro-2,4,6-trifluoromethyl aniline.

Summary of the invention

The object of the invention is to solve in prior art and fail in N-nitro substituted aniline compounds, to introduce the deficiency of three fluorine atoms, provide compound N-nitro-2,4,6-trifluoromethyl aniline simultaneously.Another two objects of the present invention are to provide the synthetic method of this compound and in the application as in plant-growth regulator effective ingredient.

For realizing above object, the present invention has adopted following technical scheme:

The compounds of this invention N-nitro-2, the structural formula of 4,6-trifluoromethyl aniline is as shown in (I):

Compound N-nitro-2, the synthetic method of 4,6-trifluoromethyl aniline, is characterized in that comprising the following steps:

(1) 2,4,6-trifluoromethyl aniline is dissolved in to toluene, makes the solution that concentration is 2mol/L, control 20 ℃ of temperature, the nitrosonitric acid toluene solution that dropping concentration is 0.6ml/ml, the mol ratio that makes 2,4,6-trifluoromethyl aniline and nitric acid is 1: 1.6, suction filtration, dry, obtain 2,4,6-trifluoromethyl aniline nitrate;

(2) by 2,4,6-trifluoromethyl aniline nitrate is dissolved in toluene, makes the solution that concentration is 0.5mol/L, control temperature 25-30 ℃, the diacetyl oxide toluene solution that drips 0.8ml/ml, makes 2,4, the mol ratio of 6-trifluoromethyl aniline nitrate and diacetyl oxide is 1: 1, after 2.5 hours, stopped reaction, reaction solution is standby;

(3) above-mentioned reaction solution being joined at ambient temperature to concentration is in 5% sodium bicarbonate aqueous solution, then controls temperature below 25 ℃, slowly drips concentrated hydrochloric acid to solution PH and reaches 1-2, and decompress filter, obtains N-nitro-2,4,6-trifluoromethyl aniline crude product;

(4), by N-nitro-2,4,6-trifluoromethyl aniline crude product repeating step (3), obtains described compound N-nitro-2,4,6-trifluoromethyl aniline.

Particularly, compou nd synthesis route of the present invention is as follows:

Compound N-nitro-2,4,6-trifluoromethyl aniline is in the application as in plant-growth regulator effective ingredient.

The invention has the beneficial effects as follows:

(1) synthetic method step is few, and technique is simple, and cost is low, and productive rate is high.

(2) N-nitro-2, the plant growth regulating successful of 4,6-trifluoromethyl aniline is better than N-nitro-2,4,6-trichloroaniline, N-nitro-2,4,6-bromamide, has highly selective to the growth regulating of rice root, and the growth to other crops under lower concentration does not have restraining effect.

Accompanying drawing explanation

Fig. 1 be the compounds of this invention proton nmr spectra ( ¹h NMR) spectrogram;

Fig. 2 is infrared spectra (IR) spectrogram of the compounds of this invention;

Fig. 3 is different concns compound N-nitro-2, and the growth regulating-activity photo of 4,6-trifluoromethyl aniline to paddy rice, is followed successively by photo from left to right: 50mg/L, 25mg/L, 10mg/L, 5mg/L, 1mg/L, acetone contrast, clear water contrast.

Fig. 4 is different concns compound N-nitro-2, and the growth regulating-activity photo of 4,6-trichloroaniline to paddy rice, is followed successively by photo from left to right: 50mg/L, 25mg/L, 10mg/L, 5mg/L, 1mg/L, acetone contrast, clear water contrast.

Fig. 5 is different concns compound N-nitro-2, the growth regulating-activity photo of 4,6-bromamide to paddy rice: be followed successively by from left to right in photo: 50mg/L, 25mg/L, 10mg/L, 5mg/L, 1mg/L, acetone contrast, clear water contrast.

Embodiment

Below in conjunction with drawings and Examples, further illustrate the present invention.

Embodiment 1

Compound N-nitro-2, the synthetic method of 4,6-trifluoromethyl aniline, comprises the following steps:

(1) in being housed, bis-mouthfuls of flasks of 150ml of magnetic agitation, thermometer and constant pressure funnel add 40ml toluene, 11.77g (0.08mol) 2,4,6-trifluoromethyl aniline (being purchased from Yetai Fine Chemical Inst., Changzhou City), 20 ℃ of water-bath temperature controls, magnetic agitation, the nitrosonitric acid that slowly dropping 6ml concentration is 98% and the mixed solution of 10ml toluene, within 20 minutes, dropwise, continue stirring reaction 30 minutes, stopped reaction.Decompress filter, uses 10ml toluene wash, obtains white powder solid, and 2,4,6-trifluoromethyl aniline nitrate, vacuum-drying, productive rate is 96%;

(2) in being housed, the 250ml there-necked flask of magnetic agitation, thermometer, constant pressure funnel and reflux condensing tube adds 100ml toluene, 10.5g (0.05mol) 2,4,6-trifluoromethyl aniline nitrate, controls temperature 25-30 ℃, slowly drip the mixed solution of 8ml diacetyl oxide and 10ml toluene, within 30 minutes, dropwise, continue reaction, precipitation fades away, reaction solution color is by colourless shiny red or the garnet of gradually becoming, after 2.5 hours, reaction solution is homogeneous phase, stopped reaction, and reaction solution is standby;

(3) in the 500ml there-necked flask of magnetic agitation, thermometer and constant pressure funnel is housed, adding 150ml concentration is 5% sodium bicarbonate aqueous solution, magnetic agitation, drips above-mentioned reaction solution under room temperature, within 10 minutes, dropwise, continue reaction 30 minutes, stopped reaction.Obtain orange-yellow transparent liquid.In being housed, bis-mouthfuls of flasks of 250ml of magnetic agitation, thermometer and constant pressure funnel add above-mentioned orange-yellow transparent liquid, magnetic agitation, ice-water bath temperature control, below 25 ℃, slowly drips concentrated hydrochloric acid, when reaching 1-2, reaction solution PH have more precipitation to produce, stopped reaction.Decompress filter, obtains light yellow or white plates or granular crystal, i.e. N-nitro-2,4,6-trifluoromethyl aniline crude product;

(4) by N-nitro-2, it is 5% sodium bicarbonate aqueous solution that 4,6-trifluoromethyl aniline crude product is dissolved in concentration, and decompress filter regulates filtrate PH to 1-2, and decompress filter, obtains sheet or granular crystal, seasoning, and productive rate is 40%.M.p.68-68.5 ℃, 25 ℃ in water solubleness be about 18mg/ml.

The compound test result synthetic according to the method is:

IR(KBr)，v(cm ^-1)：3271.28(N-H)，3090.66(Ar-H)，1620.76，1598.96，1508.65，1455.71(Ar：C＝C)，1558.48，1228.72(N-NO ₂)，1346.71，1321.80(N-O)；

¹H?NMR(600MHz，CDCl3)δ9.37(s，1H，NH)，6.84(t，2H，J＝8.1Hz，ArH)。

It is the AVATAR 330 type infrared spectrometers (KBr pressed disc method) that U.S. Nicolet company produces that infrared spectra (IR) is measured instrument, proton nmr spectra ( ¹h NMR) measuring instrument is that the Switzerland AV-600MHz of Bruker company type nuclear magnetic resonance analyser is (with d ₆-CDCl ₃for solvent, TMS is interior mark).

Embodiment 2

Compound N-nitro-2, the plant growth regulating activity test of 4,6-trifluoromethyl aniline

Test method: little agar diffusion method.

Test medicine: N-nitro-2,4,6-trifluoromethyl aniline, N-nitro-2,4,6-trichloroaniline, N-nitro-2,4,6-bromamide.

Test concentrations: 1mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L.

Test target: wheat, paddy rice, Chinese sorghum, corn, rape, three-coloured amaranth, cucumber, cotton, peanut, soya bean;

0.8% nutrient agar preparation: get 1000ml water and be heated to boiling, add 8g agar powder, after agar powder dissolves completely, be cooled to 60 ℃ of insulations, make 0.8% nutrient agar standby.

Medicament mother liquor preparation: take each target compound 0.1g and be dissolved in the acetone of 9ml, add 1ml tween 80, making concentration is the target compound liquid of 10000mg/L, adds that suitable quantity of water dilution obtains 10,50,100,250, the liquid of 5 concentration gradients of 500mg/L.

Pastille substratum preparation: get 5mL liquid to be added to the diameter that 45ml60 ℃ of nutrient agar be housed be 7cm, highly in the cultivation cup for 9cm, after fully mixing, be cooled to and solidify, obtain containing concentration and be 1,5,10,25, the nutrient agar of 50mg/L.

Test target crop seed is processed: target crop seed soaks 12 hours in 25 ℃ of water, and the seed after immersion is placed in and is lined with moistening filter paper culture dish, and at 35 ℃, vernalization is standby to the bud that shows money or valuables one carries unintentionally.

Inoculation: choose the consistent crop seed to be measured that germinates (each 10 of wheats, paddy rice, three-coloured amaranth, cucumber, each 4 of soya beans) and be placed in and be lined with the 50ml that two layers of filter paper is equipped with 5ml pastille substratum and cultivate cup.Rim of a cup, with after preservative film sealing, is pricked 20-30 hole on preservative film with syringe needle, in 25 ℃ of thermostatic chambers, cultivate 5 days.Each sample repeats 3 times, and is provided with clear water contrast, acetone solvent contrast.

Calculate: after 5 days, root length, the stem of measuring crop are long, calculate and proofread and correct root length, the impact on target plant growth with evaluation objective compound of the long short length rate of stem.

Data statistics and analysis: root length, the stem of measuring crop are long, calculate and proofread and correct root length, the impact on target plant growth with evaluation objective compound of the long short length rate of stem.The calculation formula of proofreading and correct the short long rate of root long (stem is long) is:

$R=(\frac{L_1-L_0}{L_0}-\frac{L_S-L_0}{L_0})\×100=\frac{L_1-L_S}{L_0}\×100$

In formula:

R----proofreaies and correct the short long rate of root long (stem is long);

L0----contrast root long (stem is long);

L1----processes root long (stem is long);

LS----solvent control root long (stem is long).

The drug concentration of 5mg/L of usining is active as the adjusting of normal concentration check unknown compound, and usings A, B, C, D level Four as active grading evaluation criteria.Short long rate be greater than 70% be A level, 50%-70%'s be B level, 30%-50%'s is C level, be less than 30% be D level.Compound N-nitro-2,4,6-trifluoromethyl aniline, N-nitro-2,4,6-trichloroaniline, N-nitro-2,4,6-bromamide under the dosage of 5mg/L to the active and residing rank of test plant growth in Table 1.

The plant growth regulating activity evaluation result of table 1 compound (drug concentration 5mg/L)

In table, "---" represents restraining effect

Different concns compound N-nitro-2,4,6-trifluoromethyl aniline, N-nitro-2,4,6-trichloroaniline, N-nitro-2,4,6-bromamide is shown in respectively Fig. 3,4,5 to the growth regulating-activity of paddy rice.

Interpretation of result:

(1) within the scope of test drug concentration, under lower concentration, compound N-nitro-2,4,6-trifluoromethyl aniline, N-nitro-2,4,6-trichloroaniline, N-nitro-2,4,6-bromamide has the effect of promotion growth in various degree to the root of partial test crop and stem, along with the increase of drug concentration, promoter action weakens; Under high density, compound shows as the effect of inhibition growth in various degree to the root of partial test crop and stem, and along with the increase of drug concentration, restraining effect strengthens.There is similar plants functions of hormones.

(2) compound N-nitro-2,4,6-trifluoromethyl aniline is obviously better than compound N-nitro-2 to the promoter action of the growth of the root of partial test crop under low drug concentration, 4,6-trichloroaniline and N-nitro-2,4,6-bromamide; Compound N-nitro-2,4,6-trichloroaniline and N-nitro-2,4,6-bromamide has to the root of partial test crop and stem the regulating effect that slight promotion is grown within the scope of test concentrations, the root of partial test crop and stem are shown as to the effect that suppresses growth, and along with the increase of drug concentration, restraining effect strengthens.

(3) compound N-nitro-2,4,6-trifluoromethyl aniline is better than the promoter action to the growth of stem to the promoter action of the growth of the root of five kinds of test crops under low drug concentration; Under relatively high drug concentration, obvious to the restraining effect of the test root of crop and the growth of stem.Compound N-nitro-2,4,6-trifluoromethyl aniline is fairly obvious to the promoter action of the growth of the root of paddy rice, not obvious to the promoter action of the growth of the root of other crops, not obvious to the promoter action of the growth of the stem of test crop.

(4) compound N-nitro-2,4,6-trichloroaniline does not have promoter action to the growth of the root of wheat, three-coloured amaranth, paddy rice and stem, under lower concentration, the promoter action of the growth of the stem of cucumber, soya bean is better than to the promoter action to the growth of root, but all not obvious.

(5) compound N-nitro-2,4,6-bromamide does not have promoter action to the growth of the root of wheat, paddy rice and stem, under lower concentration, the promoter action of the growth of the root of cucumber, soya bean is better than to the promoter action to the growth of stem, but all not obvious.

Known according to the plant growth regulating activity evaluation result of table 1 compound: under 5mg/L drug concentration, compound N-nitro-2,4,6-trifluoromethyl aniline is 91.7% to the short long rate of the root of paddy rice, promoter action reaches A level level; Compound N-nitro-2,4,6-trichloroaniline is 40.0% to the short long rate of the stem of soya bean, promoter action reaches C level level; Compound N-nitro-2,4,6-bromamide is 40.9% to the short long rate of the root of soya bean, promoter action reaches C level level.

In three kinds of compounds, N-nitro-2, the plant growth regulating effect of 4,6-trifluoromethyl aniline is best, and the growth regulating to the root of paddy rice, has highly selective.Meanwhile, under lower concentration, the growth to other crops does not have restraining effect; N-nitro-2,4,6-trichloroaniline and N-nitro-2, the plant growth regulating activity of 4,6-bromamide is poor, not obvious to the growth-promoting effect of the root of cucumber and soya bean and stem, can reduce the number of root of the crop simultaneously.Meanwhile, under lower concentration, the growth to other crops has restraining effect.

Claims (3)

1. compound N-nitro-2,4,6-trifluoromethyl aniline, has the structure shown in formula (I):

。

2. compound N-nitro-2, the synthetic method of 4,6-trifluoromethyl aniline, is characterized in that comprising the following steps:

(1) 2,4,6-trifluoromethyl aniline is dissolved in to toluene, makes the solution that concentration is 2mol/L, control 20 ℃ of temperature, the nitric acid toluene solution that dropping concentration is 0.6ml/ml, the mol ratio that makes 2,4,6-trifluoromethyl aniline and nitric acid is 1: 1.6, suction filtration, dry, obtain 2,4,6-trifluoromethyl aniline nitrate;

(2) by 2,4,6-trifluoromethyl aniline nitrate is dissolved in toluene, makes the solution that concentration is 0.5mol/L, control temperature 25-30 ℃, the diacetyl oxide toluene solution that drips 0.8ml/ml, makes 2,4, the mol ratio of 6-trifluoromethyl aniline nitrate and diacetyl oxide is 1: 1, after 2.5 hours, stopped reaction, reaction solution is standby;

(3) above-mentioned reaction solution being joined at ambient temperature to concentration is in 5% sodium bicarbonate aqueous solution, then controls temperature below 25 ℃, slowly drips concentrated hydrochloric acid to solution PH and reaches 1-2, and decompress filter, obtains N-nitro-2,4,6-trifluoromethyl aniline crude product;

(4), by N-nitro-2,4,6-trifluoromethyl aniline crude product repeating step (3), obtains described compound N-nitro-2,4,6-trifluoromethyl aniline.

3. compound N-nitro-2,4,6-trifluoromethyl aniline is in the application as in plant-growth regulator effective ingredient.

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