CN101607857A - The manufacture method of alcohols - Google Patents
The manufacture method of alcohols Download PDFInfo
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- CN101607857A CN101607857A CNA2008101489202A CN200810148920A CN101607857A CN 101607857 A CN101607857 A CN 101607857A CN A2008101489202 A CNA2008101489202 A CN A2008101489202A CN 200810148920 A CN200810148920 A CN 200810148920A CN 101607857 A CN101607857 A CN 101607857A
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- alcohols
- manufacture method
- aromatic
- grignard reagent
- ether
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Abstract
Problem of the present invention be to provide a kind of productivity well, obtain to have the alcohols manufacture method of the alcohols of 2 grades or 3 grades carbon with high yield.The present invention has solved above-mentioned problem by the manufacture method that following alcohols is provided, that is, and and a kind of manufacture method of alcohols, in the presence of the mixed solvent of fatty ether and aromatic organic solvent, with the Grignard reagent shown in the following chemical formula, with paraformaldehyde or formaldehyde reaction, then with product hydrolysis, R
nCH
3-n-MgX (in the formula, R represents aromatic residue or aliphatic residue or unsaturated aliphatic base, and X represents halogen atom, and n represents 2 or 3).
Description
Technical field
The alcohols of making among the present invention is the useful compound of intermediate as agricultural chemicals, medicine or electric material chemical preparations.
Background technology
The method of making alcohols by the reaction of Grignard reagent and aldehydes is generally known.For example, as the manufacture method of neopentyl alcohol, various methods are known.As an example, have under tetrahydrofuran solvent, make tertiary butyl chlorination magnesium and formaldehyde reaction, make the method for neopentyl alcohol, but yield is lower, is 42～50% (for example, non-patent literature 1).In addition, also have under tetrahydrofuran solvent, make the reaction of tertiary butyl chlorination magnesium and paraformaldehyde, make the method for neopentyl alcohol, but have the problem (for example, non-patent literature 2) that to use a large amount of solvents.
Non-patent literature 1:J.Am.Chem.Soc.2028,60 volumes (1938)
Non-patent literature 2:Org.Process.Res.Dev.825,9 volumes (2005)
Summary of the invention
The problem that invention will solve
The objective of the invention is to, the manufacture method that productivity is good, obtain to have the alcohols of 2 grades or 3 grades carbon with high yield is provided.
The method of dealing with problems
The present invention realizes that by the manufacture method of following alcohols described method is in the presence of the mixed solvent of fatty ether and aromatic organic solvent, to make the Grignard reagent shown in the following chemical formula, with paraformaldehyde or formaldehyde reaction, then with the resultant hydrolysis.
R
nCH
3-n-MgX
(in the formula, R represents aromatic residue or aliphatic residue or unsaturated aliphatic base, and X represents halogen atom, and n represents 2 or 3.)
The effect of invention
Manufacturing method according to the invention, can productivity well, obtain to have the alcohols of 2 grades or 3 grades carbon with high-level efficiency.
Embodiment
Below, be elaborated for the present invention.
In the present invention, so-called Grignard reagent is the reagent of instigating Organohalogen compounds and MAGNESIUM METAL reaction to obtain, and represents with following general formula.
R
nCH
3-n-MgX
(in the formula, R represents aromatic residue or aliphatic residue or unsaturated aliphatic base, and X represents halogen atom, and n represents 2 or 3.)
In the present invention, as Organohalogen compounds, it is tertiary butyl chloride, tert.-butyl bromide, tert.-butyl iodide, isopropyl chloride, isopropyl bromide, isopropyl iodide, 1,1-dimethyl propyl chlorine, 1,1-dimethyl propyl bromine, 1,1-dimethyl propyl iodine, 3-chloro-3-methylpentane, 3-bromo-3-methylpentane, 3-iodo-3-methylpentane, 3-chloro-3-methyl hexane, 3-bromo-3-methyl hexane, 3-iodo-3-methyl hexane, 3-chloro-3-ethylpentane, 3-bromo-3-ethylpentane, 3-iodo-3-ethylpentane, 3-chloro-3-ethyl hexane, 3-bromo-3-ethyl hexane, 3-iodo-3-ethyl hexane, 4-chloro-4-propyl group heptane, 4-bromo-4-propyl group heptane, 4-iodo-4-propyl group heptane, 4-chloro-1-amylene, 4-bromo-1-amylene, 4-iodo-1-amylene, 5-chloro-1-hexene, 5-bromo-1-hexene, 5-iodo-1-hexene, 1-chloroethyl benzene, the 1-bromo ethyl phenenyl, 1-iodine ethylbenzene, 2-(1-chloroethyl) naphthalene, 2-(1-bromotrifluoromethane) naphthalene, 2-(1-iodine ethyl) naphthalene.
In the present invention, the R of Grignard reagent represents aromatic residue or aliphatic residue or unsaturated aliphatic base, preferably lists methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, vinyl, allyl group, phenyl, naphthyl etc.In the present invention, the R of Grignard reagent, more preferably methyl.
In the present invention, the X of Grignard reagent represents halogen atom, preferably chlorine atom, bromine atoms, iodine atom, more preferably bromine atoms or chlorine atom.
In the present invention, the n of Grignard reagent represents 2 or 3, preferably 3.
In the present invention, Grignard reagent more preferably, with the represented Grignard reagent of following general formula.
(CH
3)
3CMgCl
In the present invention, reaction solvent uses the mixed solvent of fatty ether and aromatic organic solvent.
As fatty ether, can enumerate tetrahydrofuran (THF), ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ether, hexyl ether, t-butyl methyl ether, two cyclopentyl ethers, dicyclohexyl ether etc., wherein preferred tetrahydrofuran (THF).
The amount of employed fatty ether with respect to Grignard reagent, is 2.0～10.0 times of amounts (weight), more preferably 2.0～5.0 times of amounts (weight).
Aromatic organic solvent, preferably aromatic ether or aromatic hydrocarbons.
As aromatic ether, can enumerate methyl-phenoxide, phenyl ethyl ether, phenylene dimethyl ether etc., preferred especially methyl-phenoxide.
As aromatic hydrocarbons, can enumerate dimethylbenzene, ethylbenzene, isopropyl benzene, cymene, sym-trimethylbenzene etc.The sym-trimethylbenzene of optimization aromatic hydrocarbon wherein.
The amount of employed aromatic organic solvent with respect to Grignard reagent, is 0.2～10.0 times of amount (weight), more preferably 0.2～4.0 times of amount (weight).
The blending ratio of fatty ether and aromatic organic solvent is preferably fatty ether/aromatic organic solvent=15/85～98/2, and more preferably 35/65～96/4.
In the present invention, in the presence of the mixed solvent of fatty ether and aromatic organic solvent, make Grignard reagent and paraformaldehyde or formaldehyde reaction.
The paraformaldehyde that uses in this reaction or the usage quantity of formaldehyde with respect to 1 mole of Grignard reagent, are preferably 1～5 times of mole, more preferably the ratio of 1～1.5 times of mole.
The reaction method of Grignard reagent and paraformaldehyde or formaldehyde can drip Grignard reagent, also can drip paraformaldehyde.In addition, can also the paraformaldehyde pulp be dripped with solvent.
The temperature of reaction of Grignard reagent and paraformaldehyde or formaldehyde is preferably 20～100 ℃, and more preferably 40～60 ℃, the reaction times is preferably 1～12 hour, more preferably 5～10 hours.
In addition, if having moisture in this reaction reaction system, Grignard reagent and water will react, and cause yield low, so it is desirable to carry out in inert atmospheres such as nitrogen.
In the present invention, in the presence of the mixed solvent of fatty ether and aromatic organic solvent, make Grignard reagent and paraformaldehyde or formaldehyde reaction, then utilize acidic aqueous solution to make the resultant hydrolysis.Acidic aqueous solution preferably uses the aqueous solution of mineral acid, ammonium chlorides etc. such as hydrochloric acid.The alcohol that generates separates from reaction solution by separation methods such as solvent extractions, if necessary, and with method purifying such as distillations.
Embodiment 1
Below, embodiment and comparative example are shown, explain the present invention, but the present invention is not subjected to these restriction.
In the flask of the 500ml that possesses stirrer, condenser, thermometer, dropping funnel, add 26.2g (1.08 moles) MAGNESIUM METAL, 233.6g tetrahydrofuran (THF), under nitrogen atmosphere,, drip 100.0g (1.08 moles) tertiary butyl chloride by dropping funnel 40～45 ℃ of interior temperature.After the dropping, disappear until magnesium, obtained tertiary butyl chlorination magnesium in 50～55 ℃ of stirrings of interior temperature.
Then, in the flask of the 1000ml that possesses stirrer, condenser, thermometer, dropping funnel, add 95% paraformaldehyde (PFA), the sym-trimethylbenzene of 32.1g, the 64.2g tetrahydrofuran (THF) of 32.1g (1.08 moles of pure compositions), the tertiary butyl chlorination magnesium that will before obtain 45～50 ℃ of interior temperature all drips.After the dropping, stirred 4 hours for 45～50 ℃, reaction is finished in interior temperature.After reaction finished, temperature was no more than 30 ℃ like that in making, drips 15% hydrochloric acid, makes it hydrolysis, is pipetted in the separating funnel, has obtained oil reservoir.Analyze this oil reservoir, calculate reaction yield, yield is 81.4% as a result.
Then, by with this oil reservoir underpressure distillation,, obtained the water white neopentyl alcohol of 58.6g (purity 98%) as 71～73 ℃/150 cuts that hold in the palm.
The structure of this colourless transparent liquid is identified with 1H-NMR and IR.
1H-NMR(CDCl
3)：3.3(2H)、2.1(1H)、0.9(9H)
IR：3350cm
-1、2950cm
-1、2860cm
-1。
Embodiment 2
Use device similarly to Example 1, replace sym-trimethylbenzene, react under the conditions shown in Table 1 with 32.1g toluene.The results are shown in table 1.
Embodiment 3
Use device similarly to Example 1, replace sym-trimethylbenzene, react under the conditions shown in Table 1 with the 32.1g methyl-phenoxide.The results are shown in table 1.
Comparative example 1
Use device similarly to Example 1, do not use aromatic organic solvent, react under the conditions shown in Table 1.The results are shown in table 1.
[table 1]
Claims (3)
1. the manufacture method of an alcohols in the presence of the mixed solvent of fatty ether and aromatic organic solvent, makes the Grignard reagent shown in the following chemical formula, with paraformaldehyde or formaldehyde reaction, and then with the product hydrolysis,
R
nCH
3-n-MgX
In the following formula, R represents aromatic residue or aliphatic residue or unsaturated aliphatic base, and X represents halogen atom, and n represents 2 or 3.
2. the manufacture method of alcohols as claimed in claim 1, aromatic organic solvent is aromatic ether or aromatic hydrocarbons.
3. the manufacture method of alcohols as claimed in claim 1 or 2, alcohols is R
nCH
3-nCH
2OH, wherein, R represents aromatic residue or aliphatic residue or unsaturated aliphatic base, and X represents halogen atom, and n represents 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008158864A JP2010001222A (en) | 2008-06-18 | 2008-06-18 | Method for producing alcohol |
| JP158864/2008 | 2008-06-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101607857A true CN101607857A (en) | 2009-12-23 |
Family
ID=41481784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101489202A Pending CN101607857A (en) | 2008-06-18 | 2008-09-17 | The manufacture method of alcohols |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2010001222A (en) |
| CN (1) | CN101607857A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584530A (en) * | 2012-01-18 | 2012-07-18 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
| CN102850186A (en) * | 2012-09-26 | 2013-01-02 | 江苏博特新材料有限公司 | Method for preparing 3-methyl-3-buten-1-ol |
-
2008
- 2008-06-18 JP JP2008158864A patent/JP2010001222A/en active Pending
- 2008-09-17 CN CNA2008101489202A patent/CN101607857A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584530A (en) * | 2012-01-18 | 2012-07-18 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
| CN102584530B (en) * | 2012-01-18 | 2014-02-12 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
| CN102850186A (en) * | 2012-09-26 | 2013-01-02 | 江苏博特新材料有限公司 | Method for preparing 3-methyl-3-buten-1-ol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010001222A (en) | 2010-01-07 |
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Open date: 20091223 |