CN105777571B - N- acetyl group -3- Foxlene -1- amine and preparation method thereof - Google Patents

N- acetyl group -3- Foxlene -1- amine and preparation method thereof Download PDF

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CN105777571B
CN105777571B CN201610218345.3A CN201610218345A CN105777571B CN 105777571 B CN105777571 B CN 105777571B CN 201610218345 A CN201610218345 A CN 201610218345A CN 105777571 B CN105777571 B CN 105777571B
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foxlene
amine
acetyl group
reaction
silica gel
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CN105777571A (en
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赵振东
朱守记
徐士超
陈玉湘
毕良武
王婧
古研
卢言菊
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Institute of Chemical Industry of Forest Products of CAF
Research Institute of Forestry New Technology of Chinese Academy of Forestry
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Institute of Chemical Industry of Forest Products of CAF
Research Institute of Forestry New Technology of Chinese Academy of Forestry
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/06—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses 3 Foxlene of N acetyl group, 1 amine and preparation method thereof.With N, 1,8 pairs of Meng's alkane diamines of N' diacetyls are raw material, in strong protonic acid aqueous solution, at 70 DEG C 100 DEG C or be heated to reflux and stirring condition under reacted.Stratification after the completion of reaction.Upper strata yellow oily thick liquid crude on silica gel column chromatography obtains purer 3 Foxlene of N acetyl group, 1 amine.There are the present invention reaction raw materials to be relatively easy to get, mild condition, simple technological process and other advantages.

Description

N- acetyl group -3- Foxlene -1- amine and preparation method thereof
Technical field：
The present invention relates to a kind of synthetic methods of N- acetyl group -3- Foxlene -1- amine, and in particular to is urged using strong protonic acid Change N, N'- diacetyl -1,8- eliminate Meng's alkane diamines the side that one molecule acetamide forms N- acetyl group -3- Foxlene -1- amine Method.
Background technology
Amide C-N keys are the important feature primitives of the bioactive molecules such as peptide and protein in organism, therefore, many Compound with amide group is all with excellent desinsection, antibacterial, weeding, Antiphytoviral and antitumor isoreactivity, quilt It is widely used in the fields such as medicine, pesticide.In addition, many amides compounds are also important organic synthesis intermediate, normal quilt For synthesizing hetero atom or heterocyclic compound, there is particularly important application valency in industries such as chemical industry, fragrance, dyestuff and light textiles Value.
There is N- acetyl group -1- Foxlene -8- amine with the relevant similar compound of substance of the present invention, be N.G.Kozlov etc. (J.Org.Chem.USSR(Engl.Transl.)；(United States),1986,22:3.) limonene and acetonitrile are utilized Reaction gained.This method is due to generating more by-product so that product separating-purifying is highly difficult, but does not have in document report There is any information about substance N- acetyl group -1- Foxlene -8- amine of the present invention.
In view of N- acetyl group -3- Foxlene -1- amine, in the application potential of bioactivity etc., the present invention provides N- second Acyl group -3- Foxlene -1- amine and its with N, N'- diacetyl -1,8- to Meng's alkane diamines (CN105037189A, CN105294474A it is) preparation method of raw material, to develop turpentine oil high added value deep processed product and carrying out N- in a deep going way Good basis is established in application study of the acetyl group -3- Foxlene -1- amine in the fields such as medicine or pesticide.
Invention content
The object of the present invention is to provide a kind of N- acetyl group -3- Foxlene -1- amine and preparation method thereof.This method with N, N'- diacetyls -1,8- are raw material to Meng's alkane diamines, using strong protonic acid aqueous solution as medium, have easy to operate, reaction condition temperature With at low cost, less pollution and it is controllable, industrial applications prospect is preferable the advantages that.
The technical scheme is that：A kind of N- acetyl group -3- Foxlene -1- amine, structural formula are：
The method for preparing the N- acetyl group -3- Foxlene -1- amine, by N, N'- diacetyls -1,8- are to Meng's alkane diamines It is dissolved in strong protonic acid aqueous solution, heating stirring, fully reacts, after reaction stratification, upper strata yellow oily viscous fluid Body crude on silica gel column chromatography purifies to obtain N- acetyl group -3- Foxlene -1- amine.
Strong protonic acid used includes HCl, H2SO4, the wherein mass percent concentration of HCl is 2%~30%, H2SO4's Mass percent concentration is 5%~50%.
Reaction temperature is controlled in 70 DEG C~100 DEG C or reflux state.
Reaction time is 1h~15h.
When silica gel column chromatography purifies, using ethyl acetate-light petrol solution as eluant, eluent, the volume fraction of ethyl acetate is 5%~100%.
Advantageous effect
1. reaction condition of the present invention is more mild, general control is at 70 DEG C~100 DEG C until complete under reflux conditions Into.
2. present invention process process is simple, easy to operate, environmental pollution is smaller and controllable, and industrial applications prospect is preferable.
3.N- acetyl group -3- Foxlene -1- amine, system name N- (4- isopropyl -1- methylcyclohexene -3- alkene -1- bases) second Amide, structural formula are as follows：
N- acetyl group -3- Foxlene -1- amine is a kind of Foxlene amides compound, is colourless or faint yellow at normal temperatures Thick solid is made of 3- Foxlenes and acetamide two parts, containing there are two active groups：Carbon-carbon double bond and amide groups in ring Group can be used as intermediate to be applied to the industries such as medicine and pesticide, be applied after can also being modified to the two active groups In high molecular material industry.
Description of the drawings
Fig. 1 is the gas-chromatography of substance N- acetyl group -3- Foxlene -1- amine of the present invention that reaction product is crossed through separating-purifying Scheme, in figure：1# peaks be N- acetyl group -3- Foxlene -1- amine, retention time 19.27min, content 95.04%；2# peaks are Impurity component is not identified.
Fig. 2 is infrared spectrum (FT-IR) figure of substance N- acetyl group -3- Foxlene -1- amine of the present invention.
Fig. 3 is the mass spectrum (ESI of substance N- acetyl group -3- Foxlene -1- amine of the present invention+- MS) figure.
Fig. 4 is substance N- acetyl group -3- Foxlene -1- amine of the present invention1H nuclear magnetic resonance (1H NMR) figure.
Fig. 5 is substance N- acetyl group -3- Foxlene -1- amine of the present invention13C nuclear magnetic resonance (13C NMR)
Fig. 6 is the partial enlargement of Fig. 5.
Specific embodiment
The present invention is further described with reference to specific embodiment：
The synthetic method of noval chemical compound N- acetyl group -3- Foxlene -1- amine disclosed by the invention, synthetic reaction formula are：
Specific synthetic method comprises the steps of：
(1) raw material N, N'- diacetyl -1,8- are added to strong protonic acid (HCl, H to Meng's alkane diamines2SO4Deng, wherein H2SO4A concentration of 5%~50%, HCl a concentration of 2%~20%) aqueous solution in, and be stirred.
(2) reaction temperature preferably carries out heating reflux reaction between 70 DEG C~100 DEG C.
(3) strong acid used in is sulfuric acid, hydrochloric acid etc., preferred H2SO4A concentration of 5%~50%, HCl a concentration of 2% ~20%.
(4) it waits after the completion of reacting, stratification.Upper strata yellow oily liquid is N- acetyl group -3- Foxlene -1- amine Crude product.
(5) gained N- acetyl group -3- Foxlene -1- amine crude product purified by silica gel column chromatographies are isolated and purified, and eluant, eluent is The volume fraction of ethyl acetate-light petrol solution, wherein ethyl acetate is 5%~100%.
Raw material N used in the present invention, N'- diacetyls -1,8- are relatively easy preparation, preparation method to Meng's alkane diamines It is carried out with reference to the method that embodiment 1 in the patent applications of (CN105037189A, CN105294474A) such as Zhao Zhendong is recorded.
Analysis method
Gas chromatography is taken to be detected and analyzed product.Analytical conditions for gas chromatography：Shimadzu GC-2014AF type gas Chromatography, Rtx-5 types quartz capillary chromatographic column (L 30m, ID 0.25mm, 0.25 μm of film thickness), carrier gas N2Pressure is 0.6MPa, air pressure 0.6MPa, H2Pressure is 0.6MPa, and temperature program is condition：70 DEG C (holding 2min, 3 DEG C of rate/ Min) → 100 DEG C (keeping 0min, 10 DEG C/min of rate) → 270 DEG C (keeping 2min).
Embodiment 1
A concentration of 7.5% HCl/water is added in into the 1L four-hole boiling flasks equipped with thermometer, condenser pipe and mechanical agitator Solution 369mL, N, N'- diacetyls -1,8- start stirring, are heated to reflux 6h to Meng alkane diamines 101.6g (400mmol).Instead After answering, cool down reaction solution, stratification.Upper strata yellow oily liquid is taken to obtain 43.0g crude products (Huang through rotary evaporation in vacuo Color oily dope), content 78%.Crude product is isolated and purified using silica gel column chromatography, obtains the N- second that purity is 92% Acyl group -3- Foxlene -1- amine products 21.0g (107.7mmol), yield 26.9%.
Embodiment 2
It weighs in the silica gel to 100mL beakers that 50g specifications are 200~300 mesh, and adds in suitable petroleum ether (60~90 DEG C), paste is stirred into, is poured into the chromatographic column with sand core.Weigh N- acetyl group that the content that 2g embodiments 1 obtain is 78%- 3- Foxlene -1- amine crude products, with the dissolving of a small amount of eluant, eluent and loading.When the liquid level of chromatographic column will disappear, appropriate stone is added in Sand, and add eluent, eluant, eluent is ethyl acetate petroleum ether solution (VEthyl acetate︰ V60-90 DEG C of petroleum ether=3 ︰ 8)), it is tried with 10mL Pipe connects eluent, and the eluent of each test tube is analyzed using gas chromatography, merges containing high purity N-acetyl group -3- The eluent of Foxlene -1- amine, concentrated to be dried in vacuo to obtain the faint yellow thick solid products of 1.48g, purity is 95% N- Acetyl group -3- Foxlene -1- amine.FT-IR、ESI+-MS、1H NMR and13The characterize data of C NMR is as follows：
FT-IR(cm-1)：3295.40(s,νN-H)；2958.28、2918.57(s,νC-H)；1647.28(s,νC=O)； 1549.46(s,δN-H)；1445.05、1369.70(m,δC-H)；1304.16(w,νC-N)。ESI+-MS(45ev,m/z):196.06 [M+H]+,137.03[M+H-CH3CONH2]+,95.09[M+H-CH3CONH2-CH3- CH=CH2]+.1H NMR(DMSO, 500MHz),δH 7.26(1H,s,1-NHCOCH3), 5.23 (1H, m, 3-H), 2.29 (1H, d, J=17.2,2-H), 2.12- 2.18 (1H, m, 8-H), 2.05-2.10 (1H, m, 5-H), 2.0 (1H, d, J=18.6,2-H), 1.84-1.96 (2H, m, 5-H, 6-H),1.75(3H,s,1-NHCOCH3), 1.46-1.51 (1H, m, 6-H), 1.22 (3H, s, 7-H), 0.96 (6H, d, J= 6.9,9-H,10-H).13C NMR(DMSO,75MHz),δC 168.89(1-NHCOCH3),141.67(4-C),115.80(3- C),50.57(1-C),36.76(2-C),34.11(6-C),31.69(8-C),24.32(1-NHCOCH3),23.52(7-C), 22.84(5-C),21.22(10-C),21.20(9-C).
Embodiment 3
A concentration of 10% HCl is added in into the 100mL four-hole boiling flasks equipped with thermometer, condenser pipe and mechanical agitator Aqueous solution 19.9mL, N, N'- diacetyls -1,8- are heated to reflux 6h to Meng alkane diamines 5.08g (20mmol).After having reacted, treat Reaction solution cools down, and reaction solution is analyzed using gas chromatography.The result shows that the production of N- acetyl group -3- Foxlene -1- amine Rate is 48.2%.And above-mentioned reaction solution is handled by example 1 and the separation method of embodiment 2, obtain -3- pairs of N- acetyl group Meng's alkene -1- amine products 1.31g.
Embodiment 4
A concentration of 20% is added in into the 100mL four-hole boiling flasks equipped with thermometer, condenser pipe and mechanical agitator H2SO4Aqueous solution 23mL, N, N'- diacetyls -1,8- are heated to reflux 6h to Meng alkane diamines 5.08g (20mmol).After having reacted, It treats that reaction solution cools down, reaction solution is analyzed using gas chromatography.According to analysis result, N- acetyl group -3- Foxlenes -1- The yield of amine is 47.9%.And above-mentioned reaction solution is handled by example 1 and the separation method of embodiment 2, obtain N- acetyl Base -3- Foxlene -1- amine products 1.25g.
Embodiment 5
A concentration of 20% is added in into the 100mL four-hole boiling flasks equipped with thermometer, condenser pipe and mechanical agitator H2SO4Aqueous solution 23mL, N, N'- diacetyls -1,8- are to Meng alkane diamines 5.08g (20mmol), 85 DEG C of reaction 6h.After having reacted, It treats that reaction solution cools down, reaction solution is analyzed using gas chromatography.According to analysis result, N- acetyl group -3- Foxlenes -1- The yield of amine is 7.5%.
Embodiment 6
A concentration of 20% is added in into the 100mL four-hole boiling flasks equipped with thermometer, condenser pipe and mechanical agitator H2SO4Aqueous solution 23mL, N, N'- diacetyls -1,8- are to Meng alkane diamines 5.08g (20mol), 70 DEG C of reaction 6h.Reaction terminates Afterwards, it cools down, reaction solution is analyzed with gas chromatography, the results showed that the yield of N- acetyl group -3- Foxlene -1- amine is 0.7%.

Claims (4)

1. a kind of N- acetyl group -3- Foxlene -1- amine, which is characterized in that structural formula is：
2. prepare the method for N- acetyl group -3- Foxlene -1- amine described in claim 1, which is characterized in that by N, N'- diethyls Acyl group -1,8- is dissolved in strong protonic acid aqueous solution Meng's alkane diamines, heating stirring, fully reacts, after reaction stratification, Upper strata yellow oily thick liquid crude on silica gel column chromatography purifies to obtain N- acetyl group -3- Foxlene -1- amine；Reaction temperature control System is in 70 DEG C~100 DEG C or reflux state；Reaction time is 1h~15h.
3. the method according to claim 2 for preparing N- acetyl group -3- Foxlene -1- amine, which is characterized in that used is strong Bronsted acid includes HCl, H2SO4, the wherein mass percent concentration of HCl is 2%~30%, H2SO4Mass percent concentration be 5%~50%.
4. the method according to claim 2 for preparing N- acetyl group -3- Foxlene -1- amine, which is characterized in that silica gel column layer During analysis purifying, using ethyl acetate-light petrol solution as eluant, eluent, the volume fraction of ethyl acetate is 5%~100%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013034416A1 (en) * 2011-09-09 2013-03-14 Unilever N.V. Antimicrobial method and composition
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013034416A1 (en) * 2011-09-09 2013-03-14 Unilever N.V. Antimicrobial method and composition
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis of (1S,5S,8R)-8-N-acylamino-2-alkyl-4,4,8-trimethyl-3-azabicyclo[3.3.1]non-2-enes from α-pinene;Koval’skaya, S. S. ET AL.;《Zhurnal Organicheskoi Khimii》;19911231;第27卷(第4期);757-762 *

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