CN112479890B - Preparation method of nitro compound - Google Patents
Preparation method of nitro compound Download PDFInfo
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- CN112479890B CN112479890B CN202011358027.XA CN202011358027A CN112479890B CN 112479890 B CN112479890 B CN 112479890B CN 202011358027 A CN202011358027 A CN 202011358027A CN 112479890 B CN112479890 B CN 112479890B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/10—Preparation of nitro compounds by substitution of functional groups by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/26—Halogenosulfates, i.e. monoesters of halogenosulfuric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
Abstract
The invention discloses a preparation method of a nitro compound, which comprises the following preparation steps: reacting the compound 1A with the compound 1B to obtain a compound 2A; and (3) reacting the compound 2A with a nitrosation reagent to obtain a nitrocompound crude product, and purifying to obtain a nitrocompound refined product. The invention adopts the reagent with lower price as the initial raw material, obtains the final product through two steps of reactions, has mild reaction conditions in each step, has high yield of the obtained nitro compound, and can greatly reduce the cost.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of a nitro compound.
Background
Nitro compounds are hydrocarbon molecules in which one or more hydrogen atoms are nitro (-NO) 2 ) Derivatives formed after substitution. Since the nitro group is a very strong electron withdrawing group, the nitro compound has large dipole moment, large polarity and large intermolecular attraction, and the boiling point of the nitro compound is higher than that of the corresponding halohydrocarbon.
Liquid nitro compounds are good organic solvents and have a certain chemical stability, and are therefore often used as solvents or additives for some organic reactions, such as 2-nitropropane, which is used as a special solvent for ethylene and epoxy resin coatings, rocket dyes, additives for gasoline, etc., and also for organic synthesis, have a strong dissolving capacity, are excellent solvents for various cellulose derivatives, vinyl resins, etc., and at the same time, are also used as solvents for waxes, fats, dyes, etc., lubricants for grinding pigments, and cleaning and mordants for cotton fabrics.
At present, few literature reports on the synthesis of nitro compounds are provided, and the preparation method of the nitro compounds mainly comprises a propane nitration method and can also be obtained through propylene nitration. However, the reaction process of the method adopts high temperature and high pressure, the separation of products is difficult, and the environmental pollution is serious.
Therefore, a new preparation method of the nitro compound is sought, the preparation process is optimized, the production cost is reduced, and the yield is improved, so that the method has great significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of the nitro compound, which uses a reagent with lower price as a starting material, has mild reaction conditions, has high yield of the obtained nitro compound and can greatly reduce the cost. Purifying the crude product of the nitro compound with the general structure shown in the formula I obtained by the preparation method to obtain the refined product of the nitro compound with the general structure shown in the formula I.
The invention is realized by adopting the following technical scheme:
a method for preparing a nitro compound, comprising the following steps:
preparation step S1: reacting the compound 1A with the compound 1B to obtain a compound 2A;
preparation step S2: reacting the compound 2A with a nitroreagent to obtain a nitrocompound with a general structure shown in a formula I:
wherein, the compound 1A is One or more of the combinations, X is halogen, R 1 、R 2 C, saturated or unsaturated, linear or branched, containing hetero atoms or no hetero atoms, respectively 1 -C 30 One of the hydrocarbon groups;
the compound 1B is one or a combination of more of carbonyl-containing compounds, sulfonyl-containing compounds, sulfinyl-containing compounds and phosphoryl-containing compounds.
Preferably, the compound 1B is one or a combination of a plurality of sulfuric acid, sulfurous acid, carbonic acid, sulfuryl halide, thionyl halide, carbonyl halide, diphosgene, triphosgene, N' -carbonyl diimidazole, phosphoric acid and phosphorus trioxyhalide.
Preferably, the nitrating agent is nitrite, nitrous acid, NO 2 One or a combination of several of them.
Further, the compound 2A has at least one structure of an intermediate 2A1, an intermediate 2A2, an intermediate 2A3, an intermediate 2A4 and an intermediate 2A 5;
intermediate 2A1 is a compound of the general structure shown in formula II:
intermediate 2A2 is a compound of the general structure shown in formula III:
intermediate 2A3 is a compound of the general structure shown in formula IV:
intermediate 2A4 is a compound of general structure of formula v:
intermediate 2A5 is a compound of the general structure shown in formula VI:
a is one element of N, O, S;
y is one element in P, S, C; n is 1 or 2;
wherein Z is represented by the formulae IV, V and VI corresponding to the intermediates 2A3, 2A4 and 2A5 1 、Z 2 Respectively is hydrogen atom, hydroxy group, C 1 -C 30 One of hydrocarbon group, SH, OR, SR, OM, SM, halogen; OR, R in SR is saturated OR unsaturated, C containing straight chain OR branched chain, hetero atom OR no hetero atom 1 -C 30 One of the hydrocarbon groups; m in OM and SM is metal element cation, inorganic ammonium salt cation, organic ammonium salt cation, phosphonium salt cation,One of salt positive ions and onium salt positive ions;
when n=1, y=s,is->
When n=1, y=c,is->
When n=1, y=p,is->
When n=2, y=s,is->
Further, the molar ratio of the compound 1A to the compound 1B is 1:0.1-10; the molar ratio of the compound 2A to the nitrating agent is 1:0.1-10.
Further, the reaction conditions in the preparation step S1 are: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72h.
Further, the reaction conditions in the preparation step S2 are: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72h.
Further, the reaction of the preparation step S1 is performed in a first reaction solvent; the first reaction solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
Further, the reaction of the preparation step S2 is performed in a second reaction solvent; the second reaction solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
Further, the preparation method of the nitro compound further comprises the following preparation steps:
under the drying condition, dissolving the crude nitro compound in the purification solvent, carrying out low-temperature recrystallization, filtering to remove insoluble substances, and carrying out rotary evaporation and drying on the filtrate to obtain the refined nitro compound; wherein the purifying solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the reagent with lower price as the initial raw material, obtains the final product through two steps of reactions, has mild reaction conditions in each step, has high yield of the obtained nitro compound, and can greatly reduce the cost.
The whole preparation process is simple and easy to control, is beneficial to the enlarged production, shortens the reaction production period, can obtain the nitro compound with higher purity, and can effectively improve the yield of the product.
Detailed Description
The invention will be further described with reference to the following specific embodiments, which are intended to illustrate the invention in more detail by way of a few non-limiting examples. It should be noted that these examples should not be construed as limiting the scope of the invention, which may be practiced in any of the ways described in this summary. The pressure values mentioned in the patent of the invention, unless otherwise specified, are all indicated as gauge pressure. The yield in the invention refers to the percentage ratio of the actual product quality to the theoretical product quality; wherein, theoretical product quality is calculated by the reaction equation without excessive raw materials. The purification yield in the examples of the present invention refers to the number of moles of the fine nitro compound after purification divided by the number of moles of the crude nitro compound before purification.
The following are specific examples of the present invention, in which raw materials, equipment, etc. used are obtained by purchasing them, except for special restrictions.
Example 1
The preparation method of the 2-nitropropane comprises the following preparation steps:
adding 42g of compound 1A isopropanol and compound 1B sulfuric acid into a stainless steel reaction kettle in sequence, uniformly stirring the mixture according to the molar ratio of the compound 1A to the compound 1B of 1:1.1, and reacting for 24 hours at the temperature of 100 ℃ and the pressure of 0.1MPa to obtain a compound 2A;
adding sodium nitrite serving as a nitrating agent into the compound 2A, wherein the molar ratio of the compound 2A to the nitrating agent is 1:3, and reacting for 48 hours at the temperature of 60 ℃ and the pressure of 0MPa to obtain crude 2-nitropropane, and the total yield is about 73.6%;
under the condition of drying, 50g of crude 2-nitropropane is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out, insoluble matters are removed, then the filtrate is added into a rotary evaporator, rotary evaporation is carried out for 1h at about 100 ℃, and then the mixture is dried for 2h in a blast oven at 100 ℃ to obtain refined 2-nitropropane, and the purification yield is about 87.3%.
Example 2
The preparation method of the 2-nitrobutane comprises the following preparation steps:
adding 32g of compound 1A 2-butanol and compound 1B sulfuryl chloride into a stainless steel reaction kettle in sequence, uniformly stirring the mixture according to the molar ratio of the compound 1A to the compound 1B of 1:1.3, and reacting for 24 hours at the temperature of 80 ℃ and the pressure of 0.2MPa to obtain a compound 2A;
adding a nitrating reagent potassium nitrite into the compound 2A, wherein the molar ratio of the compound 2A to the nitrating reagent is 1:8, and reacting for 48 hours at the temperature of 60 ℃ and the pressure of 0.1MPa to obtain crude 2-nitrobutane, and the total yield is about 79.5%;
under the condition of drying, 50g of crude 2-nitrobutane is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out, insoluble matters are removed, then the filtrate is added into a rotary evaporator, rotary evaporation is carried out for 1h at about 100 ℃, and then the mixture is dried for 2h in a blast oven at 100 ℃ to obtain refined 2-nitrobutane, and the purification yield is about 88.1%.
Example 3
The preparation method of the 2-nitropentane comprises the following preparation steps:
118g of compound 1A 2-amyl alcohol and compound 1B triphosgene are sequentially added into a stainless steel reaction kettle, the molar ratio of the compound 1A to the compound 1B is 1:1.2, the mixture is uniformly stirred, and the mixture is reacted for 24 hours under the conditions that the temperature is 120 ℃ and the pressure is 0.3MPa, so that compound 2A is obtained;
adding a nitrosation reagent nitrous acid into the compound 2A, wherein the molar ratio of the compound 2A to the nitrosation reagent is 1:7, and reacting for 48 hours at the temperature of 60 ℃ and the pressure of 0.2MPa to obtain crude 2-nitropentane, and the total yield is about 80.1%;
under the condition of drying, 50g of crude 2-nitropentane is dissolved in 400ml of ethanol, low-temperature recrystallization is carried out, filtration is carried out, insoluble matters are removed, then the filtrate is added into a rotary evaporator, rotary evaporation is carried out for 1h at about 100 ℃, then the mixture is dried for 2h in a blast oven at 100 ℃ to obtain refined 2-nitropentane, and the purification yield is about 84.5%.
The above embodiments are only some of the preferred embodiments of the present invention, and the examples are described only for illustrating the principle of the present invention, and should not be used to limit the scope of the patent protection of the present invention. It will be apparent to those skilled in the art that various changes, modifications and alterations can be made in this invention without departing from the spirit, principles and scope of the invention, and additional features of such modifications can be employed alone or in any combination and are intended to be within the scope of the invention as defined in the claims.
Claims (9)
1. A method for preparing a nitro compound, comprising the steps of:
preparation step S1: reacting the compound 1A with the compound 1B to obtain a compound 2A;
preparation step S2: reacting the compound 2A with a nitroreagent to obtain a nitrocompound with a general structure shown in a formula I:
wherein, the compound 1A isR 1 、R 2 C, saturated or unsaturated, linear or branched, containing hetero atoms or no hetero atoms, respectively 1 -C 30 One of the hydrocarbon groups;
compound 1B is triphosgene;
the molar ratio of the compound 1A to the compound 1B is 1:1.2.
2. The method for producing a nitro compound according to claim 1, wherein the compound 2A is an intermediate 2A1;
intermediate 2A1 is a compound of the general structure shown in formula II:
a is O element;
y is C element; n is 1.
3. The method for producing nitro compound according to claim 1, wherein the nitrosating agent is nitrite, nitrous acid, NO 2 One or a combination of several of them.
4. The method for producing a nitro compound according to claim 1, wherein the molar ratio of the compound 2A to the nitrating agent is 1:0.1-10.
5. The method for producing a nitro compound according to claim 1, wherein the reaction conditions in the production step S1 are: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72h.
6. The method for producing a nitro compound according to claim 1, wherein the reaction conditions in the production step S2 are: the reaction temperature is-50 ℃ to 200 ℃, the reaction pressure is-0.05 MPa to 1MPa, and the reaction time is 0.1h to 72h.
7. The method for producing a nitro compound according to claim 1, wherein the reaction of the production step S1 is carried out in a first reaction solvent; the first reaction solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
8. The method for producing a nitro compound according to claim 1, wherein the reaction of the production step S2 is carried out in a second reaction solvent; the second reaction solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, 1, 2-dichloroethane, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
9. The method for producing a nitro compound according to any one of claims 1 to 8, further comprising the production steps of:
under the drying condition, dissolving the crude nitro compound obtained in the preparation step S2 in a purifying solvent, carrying out low-temperature recrystallization, filtering to remove insoluble substances, and carrying out rotary evaporation and drying on the filtrate to obtain a refined nitro compound; wherein the purifying solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, ethyl acetate, dimethyl carbonate, diethyl ether, acetonitrile, dioxane, N-dimethylformamide, dimethyl sulfoxide and water.
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| KR20200002720A (en) * | 2019-10-11 | 2020-01-08 | (주)에이에스텍 | A preparing method of diethylamino hydroxybenzoyl hexylbenzoate |
Non-Patent Citations (2)
| Title |
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| Preparation of nitroethane;McCombie, H.等;《Journal of the Chemical Society》;19441231;实验部分 * |
| Routes to N-vinyl-nitroimidazoles and N-vinyl-deazapurines;Clayton, Russell等;《Journal of Heterocyclic Chemistry 》;20041231;第41卷(第5期);第703页左栏 * |
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