CN106083604B - A method of by unsaturated turpentine oil monoterpene preparation 1,8- to Meng's alkane diamines - Google Patents
A method of by unsaturated turpentine oil monoterpene preparation 1,8- to Meng's alkane diamines Download PDFInfo
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
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Abstract
1,8- is prepared to the method for Meng's alkane diamines by unsaturated turpentine oil monoterpene the invention discloses a kind of.It using unsaturated turpentine oil monoterpene as raw material, is reacted under the catalysis of strong protonic acid with organic nitrile, reaction solution is neutralized to neutrality after sufficiently reacting, water-insoluble organic solvent extraction is added, collection standing organic layer is precipitated 1,8- and crystallizes to Meng's alkane diamides.By 1,8- to Meng's alkane diamides solid hydrolyzed in the polyhydric alcohol solutions of inorganic strong alkali 1,8- to Meng's alkane diamines crude product, negative pressure rectifying obtains 1,8- to Meng's alkane diamines sterling.This method obtained 1,8- is high to Meng's alkane diamines product yield, purity is good, relative to original preparation method, the method is using unsaturated turpentine oil monoterpene more cheap and easy to get as raw material, process route is simple, it can effectively reduce the production cost to Meng's alkane diamines, in addition, the present invention also has many advantages, such as that small toxicity, operating process are simple.
Description
Technical field:
The present invention relates to a kind of 1,8- for preparing to the process of Meng's alkane diamines, more particularly, to one kind by unsaturated turpentine
Oily monoterpene and organic nitrile single step reaction prepare 1,8- to Meng's alkane diamides, and preparation is then hydrolyzed in the polyhydric alcohol solutions of inorganic base
Method of the 1,8- to Meng's alkane diamines.
Background content
1,8- is a kind of to Meng's alkane diamines (4-amino- α, α, 4-trimethyl-cyclohexanemethanamine)
Monoterpene diamine derivatives are synthetics, molecular structure are as follows:
1,8- has Meng's alkane diamines and is all liquid within the scope of very big temperature and keeps low viscosity, heat-resisting, in high temperature
Its reaction will not be oxidized, there is good dissolubility in hydrocarbon oil solvent, there is high basicity and can control down
The characteristic of activity and stereoselectivity, is the important cycloaliphatic epoxy resin curing agent having determined that.In addition it can be with
Original as bacterial inhibitor and polyamide, polyurethane, silicon alcohol condensation catalyst and some new alkylation ligands in perfumed soap
Material can also improve the colouring power that polyester resin receives acid dyes to Meng's alkane diamines processing polyester resin with 1,8-.
Synthesis 1,8- existing so far has the method for Meng's alkane diamines:
(1) Newman M.Bortnick of Rohm&Haas company etc. (US2632022 (1953)) is with dipentene, terpinum
Or firpene etc. is raw material, reacts in the water phase existing for Cymag, sulfuric acid, first generates 1,8- dimethylformamide-p- Meng's alkane, so
Hydrolysis obtains purpose product 1 afterwards, and 8- has been carried out industrialized production to Meng's alkane diamines, this method, and makes Rohm&Haas company
Unique supplier as the global product.But this method is using severe poisonous chemicals Cymag as raw material, in the hydrogen cyanide of generation
Mesosome is the higher severe poisonous chemicals of security risk, and reaction toxicity is high, environmental pollution is big.
(2) A.PANCRAZI etc. (Bull Soc Chim Fr, (1-2, Pt.2), 1977:162-164) is with N3H/BF3-
Et2O is catalyst system, with australene, nopinene, terpinum or dipentene and HN3Reaction generates 1,8- diazido-p- Meng's alkane,
Then NaBH is used4Reduction obtains purpose product 1,8- to Meng's alkane diamines.The maximum shortcoming of this method be need to prepare it is special
HN3Solution, risk is very big, this method N3H/BF3-Et2O is catalyst system, and system is very sensitive to moisture, Er Qiesuo
The all organic solvents of solvent, the more serious industrialization difficult to realize of damage ratio, Practical significance are little.
(3) Zhao Zhendong etc. (CN 101085740A (2006)) reacts preparation 1,8- diazido-with terpinum with Sodium azide
P- Meng's alkane obtains 1,8- to Meng's alkane diamines by palladium charcoal hydrogenating reduction, is improved the technique of A.PANCRAZI etc., yield
Reach 89.24%, but using the Sodium azide for having explosive performance, security risk is larger, and during the reaction there are also it is easily generated can
The higher hydrazoic acid of the toxicity that can be leaked limits its plant-scale development and application.
(4) terpinum is reacted with organic nitrile and is made in organic acidic solution by clock emerging equal (CN 102746161A (2012))
1,8- is obtained 1,8- to Meng's alkane two with potassium borohydride reduction to Meng's alkane diamides after extraction and separation to Meng's alkane diamides by standby 1,8-
Amine product, reaction yield reach 92.7%.Although this method solves the high, ring to Meng's alkane diamines production technology toxicity in the past substantially
Border pollution weight, the defects of security risk is big, but 1,8- is prepared to the reaction of Meng's alkane diamides using terpinum as raw material, production cost
It is higher, and reduction reaction sodium borohydride, potassium borohydride etc. as metering reducing agent, not only at high cost but also environmental pollution also compared with
Weight.
Summary of the invention
In order to solve existing 1,8- at high cost existing for Meng's alkane diamines technology of preparing, toxicity is big, environmental pollution weight with
And process safety hidden danger it is higher the defects of, the present invention provides one kind by unsaturated turpentine oil monoterpene prepare 1,8- to Meng's alkane diamines
Method, it is acylated to carry out isomery using unsaturated turpentine oil monoterpene and the lower organic nitrile of toxicity cheap and easy to get as raw material first
Reaction, is then hydrolyzed to prepare 1,8- to Meng's alkane diamines in the aqueous slkali of polyalcohol, simplifies 1,8- to Meng's alkane diamines
Production process route, reduce production cost, reduce the harm of ambient enviroment, improve production security.
The technical solution of the present invention is as follows: a kind of prepare 1,8- to the method for Meng's alkane diamines by unsaturated turpentine oil monoterpene, make
It is raw material with unsaturated turpentine oil monoterpene, carries out Ritter amidation process preparation 1 with organic nitrile under the catalysis of strong protonic acid,
Reaction solution is neutralized to neutrality after sufficiently reacting to Meng's alkane diamides by 8-, and water-insoluble organic solvent extraction is added, collects quiet
The machine of being equipped with chromatographs out 1,8- and crystallizes to Meng's alkane diamides；1,8- crystallizes Meng's alkane diamides to the polyhydric alcohol solutions in inorganic strong alkali
Middle hydrolysis obtains 1,8- to Meng's alkane diamines crude product, and negative pressure rectifying obtains 1,8- to Meng's alkane diamines sterling.
The unsaturated turpentine oil monoterpene includes turpentine oil, australene, nopinene, industrial dipentene, limonene, α-pine tar
Alkene, γ-terpinene, terpinolene, α-phellandrene, any one or any several mixture in β-phellandrene.
The strong protonic acid include sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, in trifluoromethanesulfonic acid any one or it is any several
Kind mixed aqueous solutions.
The organic nitrile includes acetonitrile, acrylonitrile, positive valeronitrile, benzonitrile, any one in benzene acetonitrile, organic nitrile
Additional amount is 1.5~4.0 times of unsaturated turpentine oil monoterpene mole.
The water-insoluble organic solvent include ether, ester, linear paraffin, in cycloalkane any one or it is any several
Mixture.
Amidation process carries out at a temperature of 0 DEG C~100 DEG C, and the reaction time is 1~12h.
Inorganic strong alkali used includes potassium hydroxide or sodium hydroxide, and inorganic strong alkali mass percent concentration range is 20%
~60%.
The polyol solvent includes one of ethylene glycol, propylene glycol, butanediol or any several mixture.
1,8- is 150 DEG C~240 DEG C to Meng's alkane diamides hydrolysising reacting temperature, and the reaction time is 5~15h.
Vacuum pressure used is 1.33~2.67kPa when negative pressure rectifying.
Beneficial effect
1. technology of the present invention can be abandoned, existing preparation 1,8- is high to Meng's alkane diamines process costs, toxicity is big,
The defects of environmental pollution weight and higher process safety hidden danger, is suitble to multiple batches of, mass production.
2. the present invention using unsaturated turpentine oil monoterpene cheap and easy to get as raw material, passes through amide, hydrolysis amination two
1,8- is to Meng's alkane diamines for step reaction preparation, greatly reduces the production cost to Meng's alkane diamines.
Detailed description of the invention
Fig. 1 is 1,8- to Meng's alkane diacetayl amide mass spectrogram (m/z:255.05, M+H+)。
Fig. 2 is 1,8- to Meng's alkane diacetayl amide nmr spectrum (δ: 6.90~7.40, NH).
Fig. 3 is 1,8- to Meng's alkane diamines mass spectrogram (m/z:171.11, M+H+)。
Fig. 4 is 1,8- to Meng's alkane diamines hydrogen nuclear magnetic resonance spectrogram (δ: 1.42~1.50,2-, 3-, 5-, 6-Ha；1.15~
1.33,2-, 3-, 5-, 6-He,4-H；0.99,7-H；0.94,9-, 10-H).
Specific embodiment
One kind preparing 1,8- to the method for Meng's alkane diamines by unsaturated turpentine oil monoterpene, is original with unsaturated turpentine oil monoterpene
Material carries out Ritter amidation process with organic nitrile under the catalysis of strong protonic acid and prepares 1,8- to Meng's alkane diamides, to abundant
Reaction solution is neutralized to neutrality after reaction, water-insoluble organic solvent extraction is added, collects and stands 1,8- of organic layer precipitation to Meng
The crystallization of alkane diamides.By 1,8- to Meng's alkane diamides solid hydrolyzed in the polyhydric alcohol solutions of inorganic strong alkali 1,8- to Meng's alkane two
Amine crude product, negative pressure rectifying obtain 1,8- to Meng's alkane diamines sterling.Reaction equation is as follows:
Specifically includes the following steps:
Step 1: preparation of the 1,8- to Meng's alkane diamides: by the one of the unsaturated turpentine oil monoterpene of 84.3g (about 0.58mol)
Kind or several mixtures and organic nitrile are added in 1L four-hole boiling flask, and mechanical stirring to solution is uniformly mixed, under the conditions of ice-water bath
It is slowly dropped into strong protonic acid aqueous solution, certain temperature, insulation reaction 1h~12h, by reaction solution are to slowly warm up to after being added dropwise
It is neutralized to neutrality, water-insoluble organic solvent extraction is added, is collected, standing organic layer obtains 1,8- and crystallizes to Meng's alkane diamides.Its
It is middle unsaturation turpentine oil monoterpene be turpentine oil, australene, nopinene, industrial dipentene, limonene, α-terpinene, γ-terpinene,
One of terpinolene, α-phellandrene, β-phellandrene or any several mixture.Strong protonic acid solution by sulfuric acid, phosphoric acid,
The hydrotrope of p-methyl benzenesulfonic acid, one kind of trifluoromethanesulfonic acid or two kinds or more, mass concentration range are 20%~80%, are added
Enter 1.0~3.0 times that amount is unsaturated turpentine oil monoterpene mole.The type of organic nitrile is acetonitrile, positive valeronitrile, benzonitrile, benzene
One of acetonitrile or acrylonitrile, additional amount are 1.5~4.0 times of unsaturated turpentine oil monoterpene mole.It is water-insoluble organic
Solvent is one of ether, ester, linear paraffin or cycloalkane or any several mixture.Reaction temperature is 0 DEG C~100 DEG C,
Reaction time is 1~12h.
Step 2: equipped with condenser pipe, thermometer 1L four-hole boiling flask in be added 0.20mol 1,8- to Meng's alkane diamides,
A certain amount of inorganic strong alkali and polyalcohol continuously stir down and are heated to certain temperature, 5~15h of insulation reaction, after reaction will
System is down to room temperature, and negative pressure rectifying obtains 1, the 8- that purity is 95% or more to Meng's alkane diamines sterling.Inorganic strong alkali used is
Potassium hydroxide or sodium hydroxide, polyol solvent are the aqueous solution of ethylene glycol, propylene glycol, the one or any of several of butanediol,
Inorganic strong alkali mass percent concentration range is 20%~60%, and range of reaction temperature is 150 DEG C~240 DEG C, the reaction time 5
~15h, when negative pressure rectifying, vacuum pressure used was 1.33~2.67kPa.
Raw material unsaturation turpentine oil monoterpene, reaction solution, crude product, finished product etc. are carried out using capillary gas chromatography
Reaction tracking and analytical control.
The instrument and condition of the analysis of GC used in the present invention: Shimadzu 2014AF type gas chromatograph.RTX-5 quartz wool
Capillary gas chromatography column (0.25mm × 30m × 0.25 μm Φ), 70 DEG C → 130 DEG C → 270 DEG C of temperature programming, two sections of heating rates
It is respectively as follows: 3 DEG C/min and 10 DEG C/min, 260 DEG C of sample injector temperature, 260 DEG C of fid detector temperature, carrier gas N2。
Embodiment 1
84.3g turpentine oil (firpene content 94.5% (GC method), about 0.58mol) and 63.2g acetonitrile (about 1.54mol) is added
Enter in 1L reactor, mechanical stirring to solution is uniformly mixed, and the H of 225g 60% is slowly dropped under the conditions of ice-water bath2SO4Aqueous solution
(contain H2SO41.38mol), it is to slowly warm up to 75 DEG C, insulation reaction 5h after being added dropwise, after reaction, ethyl acetate is added
Extraction collects, organic layer is evaporated off crystallization is precipitated, be filtered, washed precipitate 1,8- to Meng alkane diacetayl amide 91.1g (0.36mol),
It is 98.6% that GC method, which measures content,.
Embodiment 2
50.8g (about 0.20mol) 1,8- is added in the 1L four-hole boiling flask equipped with condenser pipe, thermometer to Meng's alkane diacetyl
Amine, 40.0g sodium hydroxide (about 1.00mol) and 600mL ethylene glycol, continuously stir down and are heated to flowing back, insulation reaction 13h,
After reaction by the near room temperature of system, it is 81.9% by the molar yield that gas Chromatographic Determination is reacted, is in vacuum degree
Rectifying is carried out under 1.33~2.67kPa pressure condition obtains the 1,8- that purity is 95% or more to Meng's alkane diamines.
Embodiment 3
In addition to unsaturated turpentine oil monoterpene is dipentene, extractant is n-hexane, other operating process with embodiment 1,
1,8- is obtained to Meng alkane diacetayl amide 63.6g (0.25mol).
Except 1,8- is outside 25.4g to Meng's alkane diacetayl amide dosage, other operations pass through gas Chromatographic Determination with embodiment 2
The molar yield of reaction is 84.1%.
Embodiment 4
In addition to unsaturated turpentine oil monoterpene Wei limonene, extractant are methylene chloride, other operating process with embodiment 1,
1,8- is obtained to Meng alkane diacetayl amide 88.9g (0.35mol).
Except 1,8- is outside 101.6g to Meng's alkane diacetayl amide dosage, other operations pass through gas Chromatographic Determination with embodiment 2
The molar yield of reaction is 64.3%.
Embodiment 5
Except the H that unsaturated turpentine oil monoterpene is α-terpinene, 60%2SO4Aqueous solution 112g (contains H2SO40.69mol) outside,
Other operating process obtain 1,8- to Meng's alkane diacetayl amide with embodiment 1.
Except 1,8- is 76.2g to Meng's alkane diacetayl amide dosage, the reaction time is outside 7h, other operations pass through with embodiment 2
The molar yield of gas Chromatographic Determination reaction is 46.8%.
Embodiment 6
Except the H that unsaturated turpentine oil monoterpene is γ-terpinene, 60%2SO4Aqueous solution 292g (contains H2SO4 1.79mol)
Outside, other operating process obtain 1,8- to Meng's alkane diacetayl amide with embodiment 1.
Except 1,8- is 76.2g to Meng's alkane diacetayl amide dosage, the reaction time is outside 15h, other operations are led to embodiment 2
The molar yield for crossing gas Chromatographic Determination reaction is 70.8%.
Embodiment 7
Except unsaturated turpentine oil monoterpene is australene, reaction temperature is 40 DEG C, other operating process obtain 1 with embodiment 1,
8- is to Meng alkane diacetayl amide 53.3g (0.21mol).
In addition to sodium hydroxide concentration is 10.0g, other operations are with embodiment 2, mole reacted by gas Chromatographic Determination
Yield is 9.0%.
Embodiment 8
In addition to unsaturated turpentine oil monoterpene is nopinene, reaction temperature is 90 DEG C, other operating process are obtained with embodiment 1
1,8- is to Meng alkane diacetayl amide 20.3g (0.08mol).
In addition to sodium hydroxide concentration is 50.0g, other operations are with embodiment 2, mole reacted by gas Chromatographic Determination
Yield is 78.1%.
Embodiment 9
Except the H that acetonitrile content is 39.5g (0.96mol), 20%2SO4Aqueous solution 520g (contains H2SO41.38mol) outside,
Its operating process obtains 1,8- to Meng alkane diacetayl amide 0.8g (0.003mol) with embodiment 1.
In addition to reaction temperature is 140 DEG C, other operations are with embodiment 2, the molar yield reacted by gas Chromatographic Determination
It is 10.0%.
Embodiment 10
Except the H that acetonitrile content is 79.0g (1.92mol), 80%2SO4Aqueous solution 169g (contains H2SO41.38mol) outside,
Its operating process obtains 1,8- to Meng alkane diacetayl amide 61.6g (0.24mol) with embodiment 1.
In addition to reaction temperature is 160 DEG C, other operations are with embodiment 2, the molar yield reacted by gas Chromatographic Determination
It is 38.3%.
Embodiment 11
Except p-methyl benzenesulfonic acid saturated aqueous solution, the extractant that strong protonic acid aqueous solution is the p-methyl benzenesulfonic acid containing 1.38mol
Outside for petroleum ether, other operating process obtain 1,8- to Meng alkane diacetayl amide 41.6g (0.16mol) with embodiment 1.
In addition to reaction temperature is 56.0g potassium hydroxide (about 1.00mol), other operations pass through gas-chromatography with embodiment 2
The molar yield of measurement reaction is 86.3%.
Embodiment 12
In addition to strong protonic acid aqueous solution is 60% trifluoromethanesulfonic acid aqueous solution of the trifluoromethanesulfonic acid containing 1.38mol, Qi Tacao
Make process with embodiment 1, obtains 1,8- to Meng alkane diacetayl amide 47.7g (0.19mol).
In addition to solvent is propylene glycol, other operations obtain 1,8- to Meng's alkane diamines sterling with embodiment 2.
Embodiment 13
Except organic nitrile is positive in addition to valeronitrile, other operating process obtain 1,8- to two n-valeramide 87.9g of Meng's alkane with embodiment 1
(0.26mol)。
Except to hydrolysis material be 0.20mol 1,8- to two n-valeramide of Meng's alkane outside, it is other operation with embodiment 2, obtain 1,
8- is to Meng's alkane diamines sterling.
Embodiment 14
In addition to organic nitrile is benzonitrile, other operating process obtain 1,8- to Meng's alkane dibenzamide 68.0g with embodiment 1
(0.18mol)。
Except to hydrolysis material be 0.20mol1,8- to Meng's alkane dibenzamide outside, it is other operation with embodiment 2, obtain 1,
8- is to Meng's alkane diamines sterling.
Embodiment 15
In addition to organic nitrile is benzene acetonitrile, other operating process obtain 1,8- to Meng's alkane acetyldiphenylamine 89.5g with embodiment 1
(0.22mol)。
Except to hydrolysis material be 0.20mol1,8- to Meng's alkane acetyldiphenylamine outside, it is other operation with embodiment 2, obtain 1,
8- is to Meng's alkane diamines sterling.
Embodiment 16
In addition to organic nitrile is acrylonitrile, other operating process obtain 1,8- to Meng's alkane diacrylamine with embodiment 1.
Except being 0.20mol1 to hydrolysis material, 8- is outside butanediol to Meng's alkane diacrylamine, solvent, and other operations are the same as real
Example 2 is applied, obtains 1,8- to Meng's alkane diamines sterling.
Claims (1)
1. a kind of prepare 1,8- to the method for Meng's alkane diamines by unsaturated turpentine oil monoterpene, which is characterized in that by 84.3 g through GC
Method measures the turpentine oil of firpene content 94.5% and 63.2 g acetonitriles are added in 1 L reactor, and mechanical stirring is equal to solution mixing
It is even, it is slowly dropped into the H2SO4 aqueous solution of 225 g, 60 % under the conditions of ice-water bath, 75 DEG C are to slowly warm up to after being added dropwise, heat preservation
React 5 h, after reaction, be added ethyl acetate extraction, collect, be evaporated off organic layer be precipitated crystallization, be filtered, washed precipitate 1,
For 8- to 91.1 g of Meng's alkane diacetayl amide, it is 98.6% that GC method, which measures content,；In the 1 L four-hole boiling flask equipped with condenser pipe, thermometer
1, the 8- of 50.8 g is added to Meng's alkane diacetayl amide, 40.0 g sodium hydroxides and 600 mL ethylene glycol, continuously stirs lower heating
To reflux, system is down to room temperature after reaction by 13 h of insulation reaction, the molar yield reacted by gas Chromatographic Determination
For 81.9 %, rectifying is carried out in the case where vacuum degree is 1.33~2.67 kPa pressure conditions and obtains 1,8- pairs that purity is 95 % or more
Meng's alkane diamines.
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| US5130330A (en) * | 1990-01-31 | 1992-07-14 | G. D. Searle & Co. | Nitrogen-containing cyclohetero cycloalkylaminoaryl derivatives for cns disorders |
| CN102040525A (en) * | 2010-11-25 | 2011-05-04 | 重庆紫光化工股份有限公司 | Preparation method of menthane diamine |
| CN105037189A (en) * | 2015-06-15 | 2015-11-11 | 中国林业科学研究院林产化学工业研究所 | Method for preparing 1,8-menthane diacetyl amide from turpentine |
| CN105294474A (en) * | 2015-11-26 | 2016-02-03 | 中国林业科学研究院林产化学工业研究所 | Method for preparing menthane diacetyl amide from p-menthadiene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5130330A (en) * | 1990-01-31 | 1992-07-14 | G. D. Searle & Co. | Nitrogen-containing cyclohetero cycloalkylaminoaryl derivatives for cns disorders |
| CN102040525A (en) * | 2010-11-25 | 2011-05-04 | 重庆紫光化工股份有限公司 | Preparation method of menthane diamine |
| CN105037189A (en) * | 2015-06-15 | 2015-11-11 | 中国林业科学研究院林产化学工业研究所 | Method for preparing 1,8-menthane diacetyl amide from turpentine |
| CN105294474A (en) * | 2015-11-26 | 2016-02-03 | 中国林业科学研究院林产化学工业研究所 | Method for preparing menthane diacetyl amide from p-menthadiene |
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