CN106083604A - A kind of by unsaturated Oleum Terebinthinae monoterpene prepare 1,8 pairs the Meng alkane diamidogen method - Google Patents
A kind of by unsaturated Oleum Terebinthinae monoterpene prepare 1,8 pairs the Meng alkane diamidogen method Download PDFInfo
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- CN106083604A CN106083604A CN201610455121.4A CN201610455121A CN106083604A CN 106083604 A CN106083604 A CN 106083604A CN 201610455121 A CN201610455121 A CN 201610455121A CN 106083604 A CN106083604 A CN 106083604A
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
Abstract
The invention discloses a kind of by unsaturated Oleum Terebinthinae monoterpene prepare 1,8 pairs the Meng alkane diamidogen method.With unsaturated Oleum Terebinthinae monoterpene as raw material, reacting with organic nitrile under the catalysis of strong protonic acid, reactant liquor is neutralized to after fully reacting neutrality, add water-insoluble organic solvent extraction, collection stands organic layer and separates out 1,8 pairs of alkane diamides crystallizations in the Meng.By 1,8 pairs the Meng alkane diamides solid hydrolyze in the polyhydric alcohol solutions of inorganic strong alkali 1,8 pairs the Meng alkane diamidogen crude product, negative pressure rectification obtains 1,8 pairs the Meng alkane diamidogen sterling.Obtained by the method 1,8 pairs the Meng alkane diamidogen product yield high, purity is good, relative to original preparation method, this method is with unsaturated Oleum Terebinthinae monoterpene more cheap and easy to get as raw material, process route is simple, can effectively reduce the production cost to alkane diamidogen in the Meng, it addition, the present invention also has the advantages such as toxicity is little, operating process is simple.
Description
Technical field:
The present invention relates to one and prepare 1, the 8-process to alkane diamidogen in the Meng, especially relate to a kind of by unsaturated Lignum Pini Nodi
Oil monoterpene and organic nitrile single step reaction prepare 1, and 8-is to alkane diamides in the Meng, and in the polyhydric alcohol solutions of inorganic base prepared by hydrolysis then
The 1,8-method to alkane diamidogen in the Meng.
Background content
1,8-is a kind of to alkane diamidogen in the Meng (4-amino-α, α, 4-trimethyl-cyclohexanemethanamine)
Monoterpene diamine derivatives, for synthetics, molecular structure is:
Alkane diamidogen in the Meng is had within the scope of the biggest temperature and to be all liquid and keep low viscosity, heat-resisting, at high temperature by 1,8-
Under also will not oxidized, in hydrocarbon oil solvent, have good dissolubility, have high basicity and its reaction can be controlled
Active and stereoselective characteristic, is the important cycloaliphatic epoxy resin firming agent having determined that.Additionally it is all right
Former as the bacterial inhibitor in fancy soap and polyamide, polyurethane, silicon alcohol condensation catalyst and some new alkylation parts
Material, with 1, alkane diamidogen process in Meng polyester resin can also be improved polyester resin and accept the colouring power of acid stain by 8-.
The method of alkane diamidogen in the Meng is had by the most existing synthesis 1,8-:
(1) the Newman M.Bortnick of Rohm&Haas company etc. (US2632022 (1953)) are with dipentene, terpinum
Or pinene etc. is raw material, react in the aqueous phase that Cyanogran., sulphuric acid exist, first generate 1,8-dimethylformamide-p-alkane in the Meng, so
Rear hydrolysis obtains purpose product 1, and 8-is to alkane diamidogen in the Meng, and the method has been carried out industrialized production, and makes Rohm&Haas company
Become unique supplier of this product of the whole world.But, the method is with severe poisonous chemicals Cyanogran. as raw material, in the hydrocyanic acid of generation
Mesosome is the higher severe poisonous chemicals of potential safety hazard, and reaction toxicity is high, environmental pollution is big.
(2) A.PANCRAZI etc. (Bull Soc Chim Fr, (1-2, Pt.2), 1977:162-164) are with N3H/BF3-
Et2O is catalyst system and catalyzing, with australene, nopinene, terpinum or dipentene and HN3Reaction generation 1,8-diazido-p-alkane in the Meng,
Then NaBH is used4Reduction obtains purpose product 1,8-to alkane diamidogen in the Meng.The maximum weak point of the method be need to prepare special
HN3Solution, danger is very big, the method N3H/BF3-Et2O is catalyst system and catalyzing, and system is very sensitive to moisture, Er Qiesuo
The all organic solvents of solvent, damage ratio is more serious is difficulty with industrialization, and Practical significance is little.
(3) Zhao Zhendong etc. (CN 101085740A (2006)) with sodium azide with terpinum reaction preparation 1,8-diazido-
P-alkane in the Meng, obtains 1 by palladium charcoal hydrogenating reduction, and the technique of A.PANCRAZI etc., to alkane diamidogen in the Meng, is improved, productivity by 8-
Reaching 89.24%, but use the sodium azide having explosive performance, potential safety hazard is relatively big, and the most easily generation can in course of reaction
The hydrazoic acid that the toxicity that can leak is higher, limits its plant-scale exploitation application.
(4) Zhong Xing etc. (CN 102746161A (2012)) are in organic acidic solution, by terpinum with organic nitrile reaction system
Standby 1,8-is to alkane diamides in the Meng, and by 1 after extract and separate, 8-obtains 1 to alkane diamides potassium borohydride reduction in the Meng, and 8-is to alkane in the Meng two
Amine product, reaction yield reaches 92.7%.Although the method solves, ring high to alkane diamidogen production technology toxicity in the Meng in the past substantially
The defects such as environment pollution weight, potential safety hazard is big, but preparation 1,8-to the reaction of alkane diamides in the Meng with terpinum as raw material, production cost
Higher, and reduction reaction sodium borohydride, potassium borohydride etc. are as metering reducing agent, not only cost is high and also environmental pollution the most relatively
Weight.
Summary of the invention
In order to solve that existing 1,8-is high to the cost that the Meng, alkane diamidogen technology of preparing existed, toxicity is big, environmental pollution weight with
And the more high defect of process safety hidden danger, the invention provides one and prepared 1 by unsaturated Oleum Terebinthinae monoterpene, 8-is to alkane diamidogen in the Meng
Method, first carry out isomery with the relatively low organic nitrile of unsaturated Oleum Terebinthinae monoterpene cheap and easy to get and toxicity for raw material and be acylated
Reaction, is hydrolyzed in the aqueous slkali of polyhydric alcohol subsequently and prepares 1, and 8-, to alkane diamidogen in the Meng, simplifies 1, and 8-is to alkane diamidogen in the Meng
Production process route, reduce production cost, decrease the harm of surrounding, improve production security.
The technical scheme is that one is prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, make
It is raw material with unsaturated Oleum Terebinthinae monoterpene, under the catalysis of strong protonic acid, carries out Ritter amidation process with organic nitrile prepare 1,
Reactant liquor, to alkane diamides in the Meng, is neutralized to neutrality after fully reacting by 8-, adds water-insoluble organic solvent extraction, collects quiet
The machine of being equipped with chromatographs out 1,8-to alkane diamides crystallization in the Meng；1,8-is crystallized the polyhydric alcohol solutions at inorganic strong alkali to alkane diamides in the Meng
Middle hydrolysis obtains 1, and 8-is to alkane diamidogen crude product in the Meng, and negative pressure rectification obtains 1, and 8-is to alkane diamidogen sterling in the Meng.
Described unsaturated Oleum Terebinthinae monoterpene includes Oleum Terebinthinae, australene, nopinene, industrial dipentene, alkene, α-Oleum Pini
Any one or the most several mixture in alkene, γ-terpinene, terpinolene, α-phellandrene, β-phellandrene.
Described strong protonic acid include in sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid any one or the most several
Plant the aqueous solution of mixing.
Described organic nitrile includes any one in acetonitrile, acrylonitrile, positive valeronitrile, benzonitrile, benzene acetonitrile, organic nitrile
Addition is 1.5～4.0 times of unsaturated Oleum Terebinthinae monoterpene mole.
Described water-insoluble organic solvent include in ether, ester, linear paraffin, cycloalkane any one or the most several
Mixture.
Amidation process is carried out at a temperature of 0 DEG C～100 DEG C, and the response time is 1～12h.
Inorganic strong alkali used includes that potassium hydroxide or sodium hydroxide, inorganic strong alkali mass percent concentration scope are 20%
～60%.
Described polyol solvent includes a kind of or the most several mixture in ethylene glycol, propylene glycol, butanediol.
1,8-is 150 DEG C～240 DEG C to alkane diamides hydrolysising reacting temperature in the Meng, and the response time is 5～15h.
Vacuum pressure used during negative pressure rectification is 1.33～2.67kPa.
Beneficial effect
Technology the most of the present invention can abandon that existing preparation 1,8-is high to alkane diamidogen process costs in the Meng, toxicity big,
Environmental pollution weight and the more high defect of process safety hidden danger, be suitable for multiple batches of, production in enormous quantities.
2. the present invention is with unsaturated Oleum Terebinthinae monoterpene cheap and easy to get as raw material, by amide, hydrolysis amination two
Step reaction preparation 1,8-, to alkane diamidogen in the Meng, greatly reduces the production cost to alkane diamidogen in the Meng.
Accompanying drawing explanation
Fig. 1 is 1, and 8-is to the Meng alkane diacetayl amide mass spectrum (m/z:255.05, M+H+)。
Fig. 2 is 1, and 8-is to alkane diacetayl amide nmr spectrum in the Meng (δ: 6.90～7.40, NH).
Fig. 3 is 1, and 8-is to the Meng alkane diamidogen mass spectrum (m/z:171.11, M+H+)。
Fig. 4 is 1,8-to alkane diamidogen hydrogen nuclear magnetic resonance spectrogram in the Meng (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 embodiments
One is prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, is former with unsaturated Oleum Terebinthinae monoterpene
Material, carries out Ritter amidation process with organic nitrile under the catalysis of strong protonic acid and prepares 1, and 8-, to alkane diamides in the Meng, treats fully
Reactant liquor being neutralized to after reaction neutrality, adds water-insoluble organic solvent extraction, collect and stand organic layer precipitation 1,8-is to the Meng
Alkane diamides crystallizes.Alkane diamides solid in the Meng is hydrolyzed in the polyhydric alcohol solutions of inorganic strong alkali by 1,8-1,8-to alkane in the Meng two
Amine crude product, negative pressure rectification obtains 1, and 8-is to alkane diamidogen sterling in the Meng.Reaction equation is as follows:
Specifically include following steps:
The first step: the 1,8-preparation to alkane diamides in the Meng: by the one of unsaturated for 84.3g (about 0.58mol) Oleum Terebinthinae monoterpene
Planting or several mixture adds in 1L four-hole boiling flask with organic nitrile, mechanical agitation is to solution mix homogeneously, under the conditions of ice-water bath
It is slowly dropped into strong protonic acid aqueous solution, is to slowly warm up to uniform temperature, insulation reaction 1h～12h after dropping, by reactant liquor
Being neutralized to neutrality, add water-insoluble organic solvent extraction, collect, stand organic layer and obtain 1,8-is to alkane diamides crystallization in the Meng.Its
Middle unsaturated Oleum Terebinthinae monoterpene be Oleum Terebinthinae, australene, nopinene, industrial dipentene, alkene, α-terpinene, γ-terpinene,
A kind of or the most several mixture in terpinolene, α-phellandrene, β-phellandrene.Strong protonic acid solution by sulphuric acid, phosphoric acid,
P-methyl benzenesulfonic acid, a kind of or two kinds and the above hydrotrope of trifluoromethanesulfonic acid, mass concentration scope is 20%～80%, adds
Enter that amount is unsaturated Oleum Terebinthinae monoterpene mole 1.0～3.0 times.The kind of organic nitrile is acetonitrile, positive valeronitrile, benzonitrile, benzene
One in acetonitrile or acrylonitrile, addition is 1.5～4.0 times of unsaturated Oleum Terebinthinae monoterpene mole.Water-insoluble organic
Solvent is a kind of or the most several mixture in ether, ester, linear paraffin or cycloalkane.Reaction temperature is 0 DEG C～100 DEG C,
Response time is 1～12h.
Second step: equipped with condensing tube, thermometer 1L four-hole boiling flask in add 0.20mol 1,8-to alkane diamides in the Meng,
A certain amount of inorganic strong alkali and polyhydric alcohol, be heated to uniform temperature, insulation reaction 5～15h under continuous stirring, reaction will after terminating
System is down to room temperature, and negative pressure rectification obtains 1 that purity is more than 95%, and 8-is to alkane diamidogen sterling in the Meng.Inorganic strong alkali used is
Potassium hydroxide or sodium hydroxide, polyol solvent is a kind of or the most several aqueous solution of ethylene glycol, propylene glycol, butanediol,
Inorganic strong alkali mass percent concentration scope is 20%～60%, and range of reaction temperature is 150 DEG C～240 DEG C, and the response time is 5
～15h, vacuum pressure used during negative pressure rectification is 1.33～2.67kPa.
Raw material unsaturation Oleum Terebinthinae monoterpene, reactant liquor, thick product, finished product etc. all use capillary gas chromatography to carry out
Reaction is followed the tracks of and analytical control.
The instrument of the GC analysis used in the present invention and condition: Shimadzu 2014AF type gas chromatograph.RTX-5 quartz wool
Capillary gas chromatography post (Φ 0.25mm × 30m × 0.25 μm), temperature programming 70 DEG C → 130 DEG C → 270 DEG C, two sections of heating rates
Being respectively as follows: 3 DEG C/min and 10 DEG C/min, injector temperature 260 DEG C, fid detector temperature 260 DEG C, carrier gas is N2。
Embodiment 1
84.3g Oleum Terebinthinae (pinene content 94.5% (GC method), about 0.58mol) is added with 63.2g acetonitrile (about 1.54mol)
Enter in 1L reactor, mechanical agitation to solution mix homogeneously, it is slowly dropped into the H of 225g 60% under the conditions of ice-water bath2SO4Aqueous solution
(containing H2SO41.38mol), after dropping, it is to slowly warm up to 75 DEG C, insulation reaction 5h, after reaction terminates, add ethyl acetate
Extraction, collect, be evaporated off organic layer separate out crystallization, filter, wash precipitate 1,8-to alkane diacetayl amide 91.1g in the Meng (0.36mol),
It is 98.6% that GC method records content.
Embodiment 2
Equipped with condensing tube, thermometer 1L four-hole boiling flask in add 50.8g (about 0.20mol) 1,8-to alkane diacetyl in the Meng
It is heated under amine, 40.0g sodium hydroxide (about 1.00mol) and 600mL ethylene glycol, continuous stirring refluxing, insulation reaction 13h,
Near for system room temperature, the molar yield reacted by gas Chromatographic Determination are 81.9% after terminating by reaction, in vacuum are
Carry out rectification under 1.33～2.67kPa pressure conditions and obtain 1,8-that purity is more than 95% to alkane diamidogen in the Meng.
Embodiment 3
Except unsaturated Oleum Terebinthinae monoterpene be dipentene, extractant be in addition to normal hexane, other operating process with embodiment 1,
Obtain 1,8-to alkane diacetayl amide 63.6g in the Meng (0.25mol).
Except 1,8-is outside 25.4g to alkane diacetayl amide consumption in the Meng, and other operation, with embodiment 2, passes through gas Chromatographic Determination
The molar yield of reaction is 84.1%.
Embodiment 4
Except unsaturated Oleum Terebinthinae monoterpene be alkene, extractant be in addition to dichloromethane, other operating process with embodiment 1,
Obtain 1,8-to alkane diacetayl amide 88.9g in the Meng (0.35mol).
Except 1,8-is outside 101.6g to alkane diacetayl amide consumption in the Meng, and other operation, with embodiment 2, passes through gas Chromatographic Determination
The molar yield of reaction is 64.3%.
Embodiment 5
Except unsaturated Oleum Terebinthinae monoterpene is α-terpinene, the H of 60%2SO4Aqueous solution 112g is (containing H2SO40.69mol) outward,
Other operating process, with embodiment 1, obtains 1, and 8-is to alkane diacetayl amide in the Meng.
Except 1,8-to alkane diacetayl amide consumption in the Meng be 76.2g, the response time be outside 7h, other operation with embodiment 2, pass through
The molar yield of gas Chromatographic Determination reaction is 46.8%.
Embodiment 6
Except unsaturated Oleum Terebinthinae monoterpene is γ-terpinene, the H of 60%2SO4Aqueous solution 292g is (containing H2SO4 1.79mol)
Outward, other operating process, with embodiment 1, obtains 1, and 8-is to alkane diacetayl amide in the Meng.
Except 1,8-to alkane diacetayl amide consumption in the Meng be 76.2g, the response time be outside 15h, other operation is with embodiment 2, logical
The molar yield crossing gas Chromatographic Determination reaction is 70.8%.
Embodiment 7
Except unsaturated Oleum Terebinthinae monoterpene be australene, reaction temperature be 40 DEG C, other operating process, with embodiment 1, obtains 1,
8-is to alkane diacetayl amide 53.3g in the Meng (0.21mol).
In addition to sodium hydroxide concentration is 10.0g, other operation with embodiment 2, by gas Chromatographic Determination react mole
Productivity is 9.0%.
Embodiment 8
Except unsaturated Oleum Terebinthinae monoterpene be nopinene, reaction temperature be in addition to 90 DEG C, other operating process with embodiment 1,
1,8-is to alkane diacetayl amide 20.3g in the Meng (0.08mol).
In addition to sodium hydroxide concentration is 50.0g, other operation with embodiment 2, by gas Chromatographic Determination react mole
Productivity is 78.1%.
Embodiment 9
Except acetonitrile content is 39.5g (0.96mol), the H of 20%2SO4Aqueous solution 520g is (containing H2SO41.38mol) outward, its
Its operating process, with embodiment 1, obtains 1, and 8-is to alkane diacetayl amide 0.8g in the Meng (0.003mol).
In addition to reaction temperature is 140 DEG C, other operation is with embodiment 2, the molar yield reacted by gas Chromatographic Determination
It is 10.0%.
Embodiment 10
Except acetonitrile content is 79.0g (1.92mol), the H of 80%2SO4Aqueous solution 169g is (containing H2SO41.38mol) outward, its
Its operating process, with embodiment 1, obtains 1, and 8-is to alkane diacetayl amide 61.6g in the Meng (0.24mol).
In addition to reaction temperature is 160 DEG C, other operation is with embodiment 2, the molar yield reacted by gas Chromatographic Determination
It is 38.3%.
Embodiment 11
Except strong protonic acid aqueous solution is the p-methyl benzenesulfonic acid saturated aqueous solution containing 1.38mol p-methyl benzenesulfonic acid, extractant
Outside for petroleum ether, other operating process, with embodiment 1, obtains 1, and 8-is to alkane diacetayl amide 41.6g in the Meng (0.16mol).
In addition to reaction temperature is 56.0g potassium hydroxide (about 1.00mol), other operation, with embodiment 2, passes through gas chromatogram
The molar yield measuring reaction is 86.3%.
Embodiment 12
In addition to the 60% trifluoromethanesulfonic acid aqueous solution that strong protonic acid aqueous solution is containing 1.38mol trifluoromethanesulfonic acid, other behaviour
Process of making, with embodiment 1, obtains 1, and 8-is to alkane diacetayl amide 47.7g in the Meng (0.19mol).
In addition to solvent is propylene glycol, other operation, with embodiment 2, obtains 1, and 8-is to alkane diamidogen sterling in the Meng.
Embodiment 13
In addition to organic nitrile is positive valeronitrile, other operating process, with embodiment 1, obtains 1, and 8-is to alkane in the Meng two n-valeramide 87.9g
(0.26mol)。
Except treating that hydrolysis material is 0.20mol 1, outside 8-is to alkane in the Meng two n-valeramide, other operation, with embodiment 2, obtains 1,
8-is to alkane diamidogen sterling in the Meng.
Embodiment 14
In addition to organic nitrile is benzonitrile, other operating process, with embodiment 1, obtains 1, and 8-is to alkane dibenzamide 68.0g in the Meng
(0.18mol)。
Except treating that hydrolysis material is 0.20mol1,8-to outside Meng alkane dibenzamide, other operation, with embodiment 2, obtains 1,
8-is to alkane diamidogen sterling in the Meng.
Embodiment 15
In addition to organic nitrile is benzene acetonitrile, other operating process, with embodiment 1, obtains 1, and 8-is to alkane acetyldiphenylamine 89.5g in the Meng
(0.22mol)。
Except treating that hydrolysis material is 0.20mol1,8-to outside Meng alkane acetyldiphenylamine, other operation, with embodiment 2, obtains 1,
8-is to alkane diamidogen sterling in the Meng.
Embodiment 16
In addition to organic nitrile is acrylonitrile, other operating process, with embodiment 1, obtains 1, and 8-is to alkane diacrylamine in the Meng.
Except treat hydrolysis material be 0.20mol1,8-be outside butanediol to alkane diacrylamine in the Meng, solvent, other operation is with real
Executing example 2, obtain 1,8-is to alkane diamidogen sterling in the Meng.
Claims (10)
1. being prepared 1 by unsaturated Oleum Terebinthinae monoterpene for one kind, the 8-method to alkane diamidogen in the Meng, it is former for using unsaturated Oleum Terebinthinae monoterpene
Material, it is characterised in that carrying out Ritter amidation process with organic nitrile under the catalysis of strong protonic acid and prepare 1,8-is to alkane in the Meng two
Amide, is neutralized to neutrality after fully reacting by reactant liquor, adds water-insoluble organic solvent extraction, collects and stand organic chromatography
Go out 1,8-to alkane diamides crystallization in the Meng；By 1,8-to alkane diamides crystallization in Meng hydrolysis in the polyhydric alcohol solutions of inorganic strong alkali
Obtaining 1,8-is to alkane diamidogen crude product in the Meng, and negative pressure rectification obtains 1, and 8-is to alkane diamidogen sterling in the Meng.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, described unsaturated Oleum Terebinthinae monoterpene include Oleum Terebinthinae, australene, nopinene, industrial dipentene, alkene, α-terpinene,
Any one or the most several mixture in γ-terpinene, terpinolene, α-phellandrene, β-phellandrene.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, described strong protonic acid include in sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid, trifluoromethanesulfonic acid any one or any several mixed
The aqueous solution closed.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, described organic nitrile includes any one in acetonitrile, acrylonitrile, positive valeronitrile, benzonitrile, benzene acetonitrile, the addition of organic nitrile
Amount is 1.5～4.0 times of unsaturated Oleum Terebinthinae monoterpene mole.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, described water-insoluble organic solvent include in ether, ester, linear paraffin, cycloalkane any one or the most several mixed
Compound.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, amidation process is carried out at a temperature of 0 DEG C～100 DEG C, and the response time is 1～12h.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, inorganic strong alkali used include potassium hydroxide or sodium hydroxide, inorganic strong alkali mass percent concentration scope be 20%～
60%.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, described polyol solvent includes a kind of or the most several mixture in ethylene glycol, propylene glycol, butanediol.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, 1,8-is 150 DEG C～240 DEG C to alkane diamides hydrolysising reacting temperature in the Meng, and the response time is 5～15h.
The most according to claim 1 being prepared 1 by unsaturated Oleum Terebinthinae monoterpene, the 8-method to alkane diamidogen in the Meng, its feature exists
In, vacuum pressure used during negative pressure rectification is 1.33～2.67kPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108218714A (en) * | 2018-01-16 | 2018-06-29 | 中国林业科学研究院林产化学工业研究所 | It is a kind of that prepared by methods of the 1,8- to Meng's alkane diamines to Meng's alkane diacetayl amide by 1,8- |
| CN114471419A (en) * | 2021-12-28 | 2022-05-13 | 西安近代化学研究所 | Production device and process for preparing 1, 8-p-menthane diamine by one-step method |
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| 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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| CN108218714A (en) * | 2018-01-16 | 2018-06-29 | 中国林业科学研究院林产化学工业研究所 | It is a kind of that prepared by methods of the 1,8- to Meng's alkane diamines to Meng's alkane diacetayl amide by 1,8- |
| CN114471419A (en) * | 2021-12-28 | 2022-05-13 | 西安近代化学研究所 | Production device and process for preparing 1, 8-p-menthane diamine by one-step method |
| CN114471419B (en) * | 2021-12-28 | 2024-03-29 | 西安近代化学研究所 | Production device and process for preparing 1, 8-p-menthanediamine by one-step method |
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