CN109232261B - Preparation method of benzyl bromide compound - Google Patents
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Abstract
The invention relates to a method for producing a benzyl bromide compound (I or II), which has the advantages of high reaction yield, high product purity, less three wastes and good environmental compatibility. Has obvious economic benefit, social benefit and environmental benefit.
Description
Technical Field
The invention belongs to the field of pesticides, and particularly relates to a novel preparation process of a bactericide pyraclostrobin intermediate.
Background
Benzyl bromide (compound I or compound II) is an important intermediate in the synthesis process of the bactericide pyraclostrobin. Various synthetic methods are reported in the literature, such as patents CN107673999A, CN106187810A, CN106083722A, CN106008347A, etc. Common bromination methods: with bromine, dibromohydantoin, NBS, HBr/H in the presence of light or a catalyst2O2、NaBrO3/NaHSO3And the like brominating with a brominating reagent. The traditional bromination process has the defects of low reaction yield, low product content, large amount of three wastes, serious environmental pollution and the like.
The new bromination process of the invention well solves the main problems existing in the traditional bromination process, and has the characteristics of high conversion rate of target products, excellent product purity, small amount of three wastes, environmental protection and the like.
The novel preparation method of the pyraclostrobin intermediate (the compound I and the compound II) described in the patent is not reported in the literature.
Disclosure of Invention
The technical scheme of the invention is as follows:
1. a process for producing a benzyl bromide compound represented by the following formula (I-a), which comprises subjecting a compound represented by the formula (I-a) to condensation reaction, reduction reaction, acylation reaction and bromination reaction to obtain a compound (II).
In the formula: r1Is represented by C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl or C2-C6An alkenyl group.
Step 1, mixing o-nitrotoluene (I-a) and R1OM reacts for a period of time in the presence of a solvent, and after the reaction is finished, the compound (I-b) is prepared by water washing, drying and desolventizing;
the solvent is selected from: 1, 2-dibromo-1, 1,2, 2-tetrachloroethane, 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane, tetrachloromethane, tetrabromomethane, bromotrichloromethane, tribromoiodomethane, bromotrifluoromethane, bromochlorodifluoromethane and tribromonitromethane. Preferably tetrabromomethane, bromotrichloromethane, tribromoiodomethane, bromotrifluoromethane and bromochlorodifluoromethane, more preferably tetrabromomethane or bromotrichloromethane;
R1-OM is selected from: sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium isopropoxide, potassium isopropoxide, sodium n-butoxide, potassium n-butoxide, sodium 1-methylpropoxide, potassium 1-methylpropoxide, sodium t-butoxide, potassium t-butoxide, sodium n-pentoxide, potassium n-pentoxide, sodium allyl, potassium allyl, sodium propynyl alkoxide, potassium propynyl alkoxide;
m represents an alkali metal atom, preferably selected from: K. and (4) Na.
The reaction temperature is selected from the range of-20 ℃ to 150 ℃, and preferably from 0 ℃ to 100 ℃;
the reaction time is usually 0.1-72 hours, preferably 1-24 hours;
and 2, adding the compound (I-b), a solvent and a catalyst into a reaction kettle, stirring for reaction, dropwise adding hydrazine hydrate, keeping the temperature for reaction after dropwise adding is finished, performing suction filtration after the reaction is finished to remove the catalyst, standing for removing a water layer, removing the solvent, recrystallizing a product with petroleum ether, performing suction filtration, and drying to obtain the compound (I-c).
The solvent is selected from: ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, toluene, methanol, etc.; preferably selected from: ethanol, dichloroethane, dichloromethane, tetrahydrofuran;
the catalyst is selected from: raney nickel;
compound (I-b): the catalyst molar ratio is 1-40: 1, and is preferably selected from: 3-10: 1;
hydrazine hydrate: the catalyst is 1-40: 1, and is preferably selected from: 3-10: 1;
the reaction temperature is selected from 0-100 ℃, and is preferably selected from: 0-30 ℃;
the reaction time is selected from: 1-20 hours, preferably selected from: 4-6 hours.
And 3, adding the compound (I-c), an acid-binding agent and a reaction solvent into a reactor, dropwise adding methyl chloroformate at low temperature, keeping the temperature for reaction after the dropwise adding is finished, and finishing the reaction. Filtering, washing and drying to obtain the compound (I-d).
The acid-binding agent is selected from: sodium bicarbonate, triethylamine, pyridine, etc., preferably selected from: sodium bicarbonate;
the solvent is selected from: dichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, methanol, ethanol, and the like, preferably selected from: methylene chloride, dichloroethane, toluene, etc.;
compound (I-c): the molar ratio of sodium bicarbonate is selected from: 1: 0.8-3, preferably selected from: 1: 1.2-1.8;
compound (I-c): the mol ratio of methyl chloroformate is selected from 1: 0.8-3; preferably selected from: 1: 1-1.2;
the reaction temperature is selected from-10 to 10 ℃;
the reaction time is selected from: 2-3 hours;
and 4, adding the compound (I-d) and the hydrogen bromide-acetic acid solution into a reaction bottle, and stirring for reaction until the reaction is finished. Washing with water, extracting, drying and desolventizing to obtain the target product (II).
The reaction temperature is selected from: 0-100 ℃, preferably 30-80 ℃;
the reaction time is selected from 0.1 to 10 hours, preferably 1 to 2.5 hours.
The weight ratio of the compound (I-d) to the hydrogen bromide-acetic acid solution is selected from 1: 2-10, and is preferably selected from: 1: 3-5.
2. A process for producing a benzyl bromide compound represented by the following formula (I) which comprises subjecting a compound represented by the formula (I-b) to bromination to obtain the compound (I).
In the formula: r1Is represented by C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl or C2-C6An alkenyl group;
the operation method comprises the following steps: and adding the compound (I-b) and hydrogen bromide-acetic acid solution into a reaction flask, and stirring for reaction to finish the reaction. Washing with water, extracting, drying and desolventizing to obtain the target product (I).
The reaction temperature is selected from: 0-100 ℃, preferably 30-80 ℃;
the reaction time is selected from 0.1-10 hours, preferably 1-2.5 hours;
the weight ratio of the compound (I-b) to the hydrogen bromide-acetic acid solution is selected from 1: 2-10, and is preferably selected from: 1: 3-5.
3. The method for producing a benzyl bromide compound according to claim 1, wherein the reaction solvent in step 1 is preferably selected from the group consisting of: tetrabromomethane or bromotrichloromethane.
4. The method for producing a benzyl bromide compound according to 1 or 2, which comprises R1O is preferably selected from: methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy.
5. The method for producing a benzyl bromide compound according to claim 1, which comprises a step 2 wherein the catalyst is selected from Raney nickel; the reducing agent is selected from hydrazine hydrate.
6. The method for producing a benzyl bromide compound according to claim 1, which comprises a reaction step 3, wherein the reaction temperature is preferably from-10 to 10 ℃; the acid-binding agent is preferably selected from sodium bicarbonate.
7. The method for producing a benzyl bromide compound according to 1 or 2, wherein the bromination reaction temperature is preferably 30 to 80 ℃; the reaction time is preferably 1 to 2.5 hours.
8. The process for producing a benzyl bromide compound according to claim 4, which comprises R1O is preferably selected from methoxy and ethoxy.
Detailed Description
First, a method for producing the benzyl bromide compound represented by the formula (I-b) will be described.
A compound represented by the formula (I-b):
in the formula (I-b),
R1is represented by C1-C6Alkyl, halo C1-C6Alkyl radical, C3-C6Cycloalkyl or C2-C6An alkenyl group;
as R1C in (1)1-C6Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Methyl, ethyl, propyl, isopropyl are preferred.
As R1Halogen of (1) C1-C6Examples of the alkyl group include a trifluoromethyl group, a difluoromethyl group, a perfluoroethyl group, a 1,1, 1-trifluoroethyl group, a 1, 1-difluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluorosec-butyl group, a perfluorotert-butyl group, a perfluoropentyl group, a perfluorohexyl group, a trichloromethyl group, a 1,1, 1-trichloroethyl group, a 1,1, 1-tribromoethyl group, a tribromomethyl group, and a triiodomethyl group. Trifluoromethyl, difluoromethyl, 1,1, 1-trifluoroethyl, 1, 1-difluoroethyl are preferred.
As R1C in (1)3-C6Cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cyclopropyl and cyclobutyl are preferred.
As R1C in (1)2-C6As the alkenyl group, a vinyl group, an allyl group, a 2-butenyl group, and a 3-butenyl group are exemplified.
Examples of the alkali metal hydroxide include the following compounds.
M-OH
Wherein M represents an alkali metal atom;
examples of the alkali metal in M include a sodium atom, a potassium atom and a lithium atom. Sodium atom and potassium atom are preferred.
Examples of the compound M-OH include sodium hydroxide, potassium hydroxide and lithium hydroxide. Sodium hydroxide and potassium hydroxide are preferred.
Examples of the alkali metal hydride include sodium hydride and potassium hydride.
The alkali metal amide may be sodium amide or potassium amide.
The solvent used for the reduction reaction (step 2) is selected from: n, N-dimethylformamide, N-dimethylacetamide, acetonitrile, benzonitrile, methanol, isopropanol, N-propanol, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, ethyl propionate, toluene, xylene, chlorobenzene, pyridine, 2-chloropyridine, 3-methylpyridine, dichloromethane, dichloroethane, petroleum ether, cyclohexane, methylcyclohexane, dimethyl sulfoxide, sulfolane, acetone, butanone, methyl isobutyl ketone, these solvents being used alone or in a mixture with one or more other solvents. Preferably selected from: methylene chloride, dichloroethane, toluene, and the like. Preferably selected from: ethanol, dichloroethane, dichloromethane, tetrahydrofuran;
the solvent used for the acylation reaction (step 3) is selected from: n, N-dimethylformamide, N-dimethylacetamide, acetonitrile, benzonitrile, methanol, isopropanol, N-propanol, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethyl acetate, ethyl propionate, toluene, xylene, chlorobenzene, pyridine, 2-chloropyridine, 3-methylpyridine, dichloromethane, dichloroethane, petroleum ether, cyclohexane, methylcyclohexane, dimethyl sulfoxide, sulfolane, acetone, butanone, methyl isobutyl ketone, these solvents being used alone or in a mixture with one or more other solvents. Preferably selected from: methylene chloride, dichloroethane, toluene, and the like.
The amount of the compound (I-b) used is usually 1 to 100 moles, preferably 1 to 10 moles, based on 1 mole of Raney nickel.
The amount of hydrazine hydrate used is usually 1 to 100 moles, preferably 1 to 10 moles, based on 1 mole of raney nickel.
The amount of sodium hydrogencarbonate used is usually 0.8 to 10 mol, preferably 1 to 2 mol, based on 1 mol of the compound (I-c).
The amount of methyl chloroformate used is usually 0.8 to 10 moles, preferably 1 to 2 moles, based on 1 mole of compound (I-c).
The reaction may be carried out under a nitrogen atmosphere.
The reaction temperature is usually in the range of-20 ℃ to 150 ℃, preferably in the range of 0 ℃ to 100 ℃. The reaction time is usually 0.1 to 72 hours, preferably 1 to 24 hours.
The reaction can be carried out while removing by-products formed accompanying the reaction to the outside of the reaction system.
After the reaction is completed, the resulting reaction mixture is concentrated, whereby benzyl bromide (compound I or compound II) can be removed. An acid or ammonium chloride may be added to the obtained reaction mixture as necessary.
Examples of the acid include hydrogen chloride and sulfuric acid.
The obtained benzyl bromide compound can be purified by a common purification means such as washing, distillation, column chromatography, etc.
The raw materials required in the reaction are all obtained by market purchase except for other specifications.
Examples
EXAMPLE 12 preparation of methoxymethyl-1-nitrobenzene
To a mixture of 23g of o-nitrotoluene and 56g of bromotrichloromethane at 70 ℃ was added dropwise 116.3g of a 28% sodium methoxide-methanol solution over 8 hours under a nitrogen atmosphere. After the addition was complete, the resulting mixture was stirred at 70 ℃ for a further 3 hours. The resulting reaction mixture was concentrated, and water was added to the residue to conduct extraction with toluene. The resulting organic layer was concentrated under reduced pressure to give 24.5g of an orange oil in 92% yield.
EXAMPLE 2 preparation of N- (2-methoxymethylphenyl) hydroxylamine
Under the nitrogen atmosphere, 34g of 2-methoxymethyl-1-nitrobenzene, 10g of ethanol, 120g of dichloroethane and 5g of raney nickel are added into a four-mouth reaction bottle, stirred and cooled to 0 ℃, 35g of hydrazine hydrate with the concentration of 85% is dripped, and after the dripping is finished, the heat preservation reaction is carried out for 6 hours at the temperature of 2 ℃. Cooling, filtering to remove solid catalyst, standing, removing water layer, removing ethanol and dichloroethane by vacuum rotary evaporation to obtain orange oily substance, recrystallizing with petroleum ether, filtering, and oven drying to obtain 29.2g product with yield of 92.5% and content of 97%.
EXAMPLE 3 preparation of methyl N-hydroxy-N- (2-methoxymethylphenyl) carbamate
Under the atmosphere of nitrogen, 30.6g of 30.6g N- (2-methoxymethylphenyl) hydroxylamine, 33.6g of sodium bicarbonate and 150g of dichloromethane are cooled to 8 ℃, 24.6g of methyl chloroformate is slowly dripped, after the dripping, the reaction is carried out for 2 hours under the condition of heat preservation, after the reaction is finished, the product N-hydroxy-N- (2-methoxymethylphenyl) methyl carbamate is obtained by filtering, washing, drying, desolventizing and crystallizing, wherein the yield is 94.7 percent and the purity is 98 percent.
EXAMPLE 4 preparation of methyl N-hydroxy-N- (2-bromomethylphenyl) carbamate
26g of methyl N-hydroxy-N- (2-methoxymethylphenyl) carbamate, 40ml of acetic acid and 40ml of a 25% hydrogen bromide-acetic acid solution were put into a 250ml four-necked reaction flask under a nitrogen atmosphere, and the temperature was raised to 65 ℃ to stir and react for 2 hours. After completion of the reaction, the reaction mixture was poured into 200g of saturated brine, extracted with ethyl acetate, and the organic layer was washed with a saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 30g of methyl N-hydroxy-N- (2-bromomethylphenyl) carbamate in 93.8 yield and 98.1% purity.
EXAMPLE 52 Synthesis of bromomethylnitrobenzene
Under nitrogen atmosphere, 16.7g of 2-methoxymethyl-1-nitrobenzene, 20ml of acetic acid, and 20ml of 25% hydrogen bromide-acetic acid solution were put into a 250ml four-necked reaction flask, and the temperature was raised to 65 ℃ to stir and react for 2 hours. After completion of the reaction, the reaction mixture was poured into 100g of saturated brine, extracted with ethyl acetate, and the organic layer was washed with a saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate. Vacuum concentration is carried out to obtain 20.6 g of 2-bromomethyl nitrobenzene, the yield is 95.1 percent, and the purity is 98 percent.
EXAMPLE 62 Synthesis of ethoxymethyl-1-nitrobenzene
To a mixture of 30g of o-nitrotoluene and 56g of tetrabromomethane, 116.3g of a 28% sodium ethoxide-ethanol solution was added dropwise at 70 ℃ over 8 hours under a nitrogen atmosphere. After the addition was complete, the resulting mixture was stirred at 70 ℃ for a further 3 hours. The resulting reaction mixture was concentrated, and water was added to the residue to conduct extraction with toluene. The organic layer was concentrated under reduced pressure to give 34.1g of an orange oil, yield 86%, purity 97%.
EXAMPLE 7 Synthesis of preparation of N- (2-methoxymethylphenyl) hydroxylamine
70g of 2-methoxymethyl-1-nitrobenzene, 31.2g of ammonium chloride solid and 150ml of water were put into a 500ml four-necked flask under a nitrogen atmosphere, stirred so that ammonium chloride was completely dissolved in water, 66g of zinc powder was added in portions, the temperature was maintained at 50 ℃, and after the zinc powder charge was completed, the reaction was continued for 30 minutes. After the reaction is finished, filtering the zinc powder by hot water, extracting by ethyl acetate, washing an organic phase by saturated saline solution, drying by anhydrous sodium sulfate, and desolventizing to obtain the N- (2-methoxy methyl phenyl) hydroxylamine.
EXAMPLE 8 Synthesis of methyl N-hydroxy-N-2- [ N- (p-chlorophenyl) pyrazol-3-oxy ] phenyl carbamate
Under the nitrogen atmosphere, 19.4g of 1- (4-chlorophenyl) -3-pyrazole alcohol and 6.9g of anhydrous potassium carbonate 80ml of methanol are heated and refluxed for reaction for 2 hours, and the methanol is removed after the solution is clear and transparent. 26g N-hydroxy-N- (2-bromomethylphenyl) methyl carbamate and 60g of N, N-dimethylformamide are added, the temperature is kept at 60 ℃ for 2 hours for reaction, the reaction is decompressed and desolventized after the reaction is finished, 60g of water and 100g of ethyl acetate are added for extraction and layering, and 34.3g of N-hydroxy-N-2- [ N- (p-chlorophenyl) pyrazole-3-oxyl ] phenyl methyl carbamate is obtained through drying, desolventization and crystallization, the yield is 91.8 percent, and the purity is 97.2 percent.
Claims (18)
1. A preparation method of a benzyl bromide compound is characterized in that a compound shown in a formula (I-a) is subjected to condensation reaction, reduction reaction, acylation reaction and bromination reaction to prepare a compound (II);
step 1, mixing o-nitrotoluene (I-a) and R1OM reacts for a period of time in a certain solvent, and after the reaction is finished, the compound (I-b) is prepared by water washing, drying and desolventizing;
the solvent is selected from: 1, 2-dibromo-1, 1,2, 2-tetrachloroethane, 1, 2-dibromo-1, 1,2, 2-tetrafluoroethane, tetrachloromethane, tetrabromomethane, bromotrichloromethane, tribromoiodomethane, bromotrifluoromethane, bromochlorodifluoromethane and tribromonitromethane;
R1-OM is selected from: sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium propoxide, potassium propoxide, sodium isopropoxide, potassium isopropoxide, sodium n-butoxide, potassium n-butoxide, sodium 1-methylpropoxide, potassium 1-methylpropoxide, sodium tert-butoxide, potassium tert-butoxide, sodium n-pentoxide, potassium n-pentoxide, sodium allyl, potassium allyl;
the reaction temperature is selected from the range of-20 ℃ to 150 ℃;
the reaction time is 0.1-72 hours;
step 2, adding the compound (I-b), a solvent and a catalyst into a reaction kettle, stirring for reaction, dropwise adding hydrazine hydrate, keeping the temperature for reaction after dropwise adding, performing suction filtration after the reaction is finished to remove the catalyst, standing for removing a water layer, removing the solvent, recrystallizing a product with petroleum ether, performing suction filtration, and drying to obtain a compound (I-c);
the solvent is selected from: ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, toluene, methanol; the catalyst is selected from: raney nickel;
compound (I-b): the molar ratio of the catalyst is selected from = 1-40: 1;
hydrazine hydrate: the catalyst = 1-40: 1;
the reaction temperature is selected from 0-100 ℃;
the reaction time is selected from: 1-20 hours;
step 3, adding the compound (I-c), an acid-binding agent and a reaction solvent into a reactor, dropwise adding methyl chloroformate at low temperature, keeping the temperature for reaction after the dropwise adding is finished, and finishing the reaction; filtering, washing and drying to obtain a compound (I-d);
the acid-binding agent is sodium bicarbonate;
the solvent is selected from: dichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, methanol, ethanol;
compound (I-c): the molar ratio of sodium bicarbonate is selected from: 1: 0.8-3;
compound (I-c): the mol ratio of methyl chloroformate is selected from 1: 0.8-3;
the reaction temperature is selected from-10 to 10 ℃;
the reaction time is selected from: 2-3 hours;
step 4, adding the compound (I-d) and hydrogen bromide-acetic acid solution into a reaction bottle, and stirring for reaction until the reaction is finished; washing with water, extracting, drying and desolventizing to obtain a target product (II);
the reaction temperature is selected from: 0-100 ℃;
the reaction time is selected from 0.1-10 hours;
the weight ratio of the compound (I-d) to the hydrogen bromide-acetic acid solution is 1: 2-10.
2. The method for preparing a benzyl bromide compound according to claim 1, wherein the solvent used in step 1 is selected from the group consisting of: tetrabromomethane, bromotrichloromethane, tribromoiodomethane, bromotrifluoromethane and bromochlorodifluoromethane.
3. The method for preparing a benzyl bromide compound according to claim 2, wherein the solvent in step 1 is tetrabromomethane or bromotrichloromethane.
4. The method for preparing a benzyl bromide compound according to claim 1, wherein the reaction temperature in step 1 is in the range of 0 to 100 ℃.
5. The method for preparing a benzyl bromide compound according to claim 1, wherein the reaction time in the step 1 is 1 to 24 hours.
6. The method for preparing a benzyl bromide compound according to claim 1, wherein the solvent used in step 2 is selected from the group consisting of ethanol, dichloroethane, dichloromethane, and tetrahydrofuran.
7. The method for preparing a benzyl bromide compound according to claim 1, wherein in the step 2, the ratio of compound (I-b): the molar ratio of the catalyst is 3-10: 1.
8. The method for preparing a benzyl bromide compound according to claim 1, wherein, in the step 2, the ratio of hydrazine hydrate: the catalyst = 3-10: 1.
9. The method for preparing a benzyl bromide compound according to claim 1, wherein the reaction temperature in the step 2 is 0 to 30 ℃.
10. The method for preparing a benzyl bromide compound according to claim 1, wherein the reaction time in step 2 is 4 to 6 hours.
11. The method for preparing a benzyl bromide compound according to claim 1, wherein the solvent of step 3 is selected from the group consisting of dichloromethane, dichloroethane and toluene.
12. The method for preparing a benzyl bromide compound according to claim 1, wherein in the step 3, the compound (I-c): the molar ratio of sodium bicarbonate is selected from: 1: 1.2-1.8.
13. The method for preparing a benzyl bromide compound according to claim 1, wherein in the step 3, the compound (I-c): the molar ratio of methyl chloroformate is selected from: 1: 1-1.2.
14. The method for preparing a benzyl bromide compound according to claim 1, wherein the reaction temperature in the step 4 is selected from 30 to 80 ℃.
15. The method for preparing a benzyl bromide compound according to claim 1, wherein the reaction time in the step 4 is selected from 1 to 2.5 hours.
16. The method for preparing a benzyl bromide compound according to claim 1, wherein the weight ratio of the compound (I-d) to the hydrogen bromide-acetic acid solution in the step 4 is selected from: 1: 3-5.
17. The method for producing the benzyl bromide compound according to any one of claims 1 to 16, wherein R is1-O is selected from: methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy.
18. The method for producing a benzyl bromide compound according to claim 17, wherein R is1-O is selected from methoxy, ethoxy.
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