CN107721862A - The synthetic method of the adamantyl ammonium halide of N, N, N trimethyl 1 - Google Patents
The synthetic method of the adamantyl ammonium halide of N, N, N trimethyl 1 Download PDFInfo
- Publication number
- CN107721862A CN107721862A CN201710964351.8A CN201710964351A CN107721862A CN 107721862 A CN107721862 A CN 107721862A CN 201710964351 A CN201710964351 A CN 201710964351A CN 107721862 A CN107721862 A CN 107721862A
- Authority
- CN
- China
- Prior art keywords
- trimethyl
- adamantyl ammonium
- synthetic method
- ammonium halides
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C**C([C@@](C1)*2)/C=C(\C)/C(C3)[C@]33C1=C2*3C Chemical compound C**C([C@@](C1)*2)/C=C(\C)/C(C3)[C@]33C1=C2*3C 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
Abstract
The invention discloses N, N, the synthetic method of the adamantyl ammonium halide of N trimethyls 1, it first in autoclave, adds 1 halo adamantane, trimethylamine and organic solvent by proportional quantity, is heated to 50 ~ 250 DEG C, confined reaction 12 ~ 48 hours, obtains reaction solution；Obtained reaction solution is cooled to room temperature again, is filtrated to get N, N, the adamantyl ammonium halide crude product of N trimethyls 1, with producing white sterling N, N, the adamantyl ammonium halide of N trimethyls 1 after organic solvent washing.The present invention is by using 1 halo adamantane and trimethylamine or its hydrochloride as initiation material, in voltage-resistant reactor（That is autoclave）In directly backflow obtain the adamantyl ammonium halide of product N, N, N trimethyl 1, compared with literature method, it has the advantages that, and few reactions steps, technique milder, cost be low, high income, and its high income is up to more than 93%.
Description
Technical field
The present invention relates to N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides.
Background technology
Quarternary ammonium salt compound is a kind of important fine chemicals, be detergent, bactericide, antistatic additive, softening agent and
The main component of template etc., it is widely used in the neck such as chemical product, automobile, weaving, electronics, biomedicine, pharmacy, new material
Domain.Meanwhile adamantane（Adamantane）With high degree of symmetry, the cage structure of high rigidity and nonpoisonous and tasteless, good lubrication
Property, heat endurance, hydrocarbon density is big, the fat-soluble peculiar property such as good (Inorg. Chem., 1996, 35, 6337.), curing
Medicine, functional polymer, lubricant, surfactant, catalyst, photographic material etc. tool have been widely used, and are described as new
Generation fine chemical material (J. Supercrit. Fluids,2002, 23, 209.).With nonpoisonous and tasteless, high rigidity Buddha's warrior attendant
Groups, as hydrophobic chain, it is several can to design synthesis instead of the straight-chain hydrocarbons in conventional quaternary ammonium salts surfactant molecule or aromatic hydrocarbon
Various types of surfactants, and assign surfactant extremely unique performance or special function, as molecular recognition,
Supramolecular self assembly, yarn fabric are submissive, antibacterial, (the Mater. Lett. 2008,62,3450. such as antiviral, antistatic;
Nanomed-Nanotechnol. Biol. Med. 2009, 5, 443.).It is reported that wherein trimethyl amantadine quaternary ammonium
Salt acts not only as antiviral drug (chemistry world, 2010,51,424.), the also industrially cause as molecular sieve
Hole agent (J. Catal., 2000,196,262.), the size of hole is controlled, prepares the catalyst for being suitable for petrochemical industry
Carrier；In addition, the important intermediate of itself or synthesizing amantadine quaternary ammonium base, quaternary ammonium base be also widely used as phase transfer catalyst,
Surfactant, detergent, bactericide, antistatic additive, the template etc. (CN103420857,2013-12-04.) of molecular sieve.
Therefore, the development potentiality of trimethyl amantadine quaternary ammonium salt is larger, and its synthetic method and application just cause people's extensive concern.
Mainly there are two kinds of approach on N, N, the synthesis of N- trimethyl -1- adamantyl ammonium halides, the route of document report：
1. using amantadine or its hydrochloride as initiation material, first and methylating reagent (such as iodomethane, dimethyl suflfate, formaldehyde-first
Acid system) carry out reaction generation N, N- dimethyl -1- amantadines, then occur again with iodomethane, bromomethane etc. quaternized anti-
It should obtain N, N, N- trimethyl -1- adamantyls ammonium halide (chemistry world, 2010,51,424; CN101935286,
2011-01-05; JP 2011051976, 2011-03-17; CN102115448, 2011-07-06.).2. with halo gold
Firm alkane be initiation material, first generates N with dimethylamine reaction, N- dimethyl -1- amantadines, then with halide（Iodomethane,
Bromomethane）Reaction, N, N, N--1-adamantyl quaternary ammonium salts of trimethyl is made（CN101935286, 2011-01-05）.
,
In above-mentioned route, it is both needed to that intermediate N, N- dimethyladamantane amine is first made, reaction time length, and the material is oily liquid
Body, purification is relatively cumbersome, and product quality is impacted；When amantadine is tertiary-aminated, using iodomethane or dimethyl suflfate as first
Base reagent intermediate yield is low, and iodomethane volatility is big and price is high, and dimethyl suflfate toxicity is big, with formaldehyde-formic acid system
Yield is higher when methylating but technique is more complicated；In second step quaterisation, bromomethane is that gas is not easy to operate, and iodomethane is waved
The big and price of hair property is high.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the present invention to provide a kind of reaction process it is stable, operate compared with
For easy, high income N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides.
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that comprise the following steps：
1）In autoclave, the organic solution of 1- halos adamantane and trimethylamine is added by proportional quantity, is heated to 50 ~ 250 DEG C, it is close
Close reaction 12 ~ 48 hours, obtain reaction solution；
2）By step 1）Reaction solution be cooled to room temperature, be filtrated to get N, N, N- trimethyl -1- adamantyl ammonium halide crude products, use
White sterling N, N, N- trimethyl -1- adamantyl ammonium halides are produced after organic solvent washing；
Its synthetic route is as follows：
。
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step 1）In three
Methylamine feed postition has two kinds：Front three amine gas are passed through in 1- halos adamantane and organic solvent mixed liquor by a；B is first by front three
Amine hydrochlorate carries out quaternization and is filtrated to get trimethylamine organic solution in organic solvent with alkali hydroxide metal, adds
In 1- halo adamantane.
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that alkali hydroxide metal
For sodium hydroxide or potassium hydroxide.
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that organic solvent be C1 ~
Any one or more mixture in C8 alcohol, ether, ester, alkane, aromatic hydrocarbons, halogenated hydrocarbons.
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that organic solvent is second
Alcohol, isopropanol, methyl tertiary butyl ether(MTBE), 1,4- dioxane, ethyl acetate, n-hexane, hexamethylene, toluene, dimethylbenzene, three chloromethanes
Any one or more mixture in alkane, dichloroethanes etc..
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that organic solvent is different
Any one or more mixture in propyl alcohol, 1,4- dioxane, ethyl acetate, hexamethylene, toluene, dichloroethanes etc..
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step 1）In 1-
The mass ratio of halo adamantane and organic solvent is 1:2.0~20, preferably 1:4.0~10.
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step 1）In 1-
The ratio between amount for the material that feeds intake of halo adamantane and trimethylamine is 1:1.2~20, preferably 1:2.0~10.
Described N, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step 2）Middle washing
Any one or more mixture in ketone, ester, alkane and halogenated hydrocarbons that organic solvent is C1 ~ C8, preferably acetone, fourth
Any one or more mixture in ketone, ethyl acetate, n-hexane, hexamethylene, chloroform, dichloroethanes etc., more preferably
For acetone, ethyl acetate, hexamethylene or chloroform.
The present invention is by using 1- halos adamantane and trimethylamine or its hydrochloride as initiation material, in voltage-resistant reactor（I.e.
Autoclave）In directly backflow obtain product N, N, N- trimethyl -1- adamantyl ammonium halides, compared with literature method, it has
The advantages that reactions steps are few, technique milder, cost are low, high income, its high income is up to more than 93%.
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
In 250 mL autoclaves, 21.5g is added（0.1 mol）1- bromos adamantane and 100 g isopropanols, into above-mentioned solution
24.0g is passed through in 30min（0.4 mol）Front three amine gas, enclosed system, it is heated to reaction at 100 DEG C and continues reaction 20 hours；
Reaction terminates, and reaction solution is cooled to room temperature, filtering, is washed to obtain white N, N, N- trimethyl -1- adamantyl brominations with acetone
Ammonium 23.9g, yield 87.2%.
1H NMR (500 MHz, D2O) δ 2.84 (s, 9H), 2.17 (s, 3H), 1.93 (s, 6H), 1.59
(d, J=12.5Hz, 3H), 1.52(d, J=12.5 Hz, 3H)。
Embodiment 2
In 250 mL autoclaves, 17.1g is added（0.1 mol）1- chloros adamantane and 140 g Isosorbide-5-Nitraes-dioxane, up
State and be passed through 35.5g in solution in 30min（0.6 mol）Front three amine gas, enclosed system, it is heated to reaction at 110 DEG C and continues instead
Answer 30 hours；Reaction terminates, and reaction solution is cooled to room temperature, filtering, is washed to obtain white N, N, N- trimethyls -1- with ethyl acetate
Adamantyl ammonium chloride 19.9g, yield 86.7%.1H NMR (500 MHz, D2O) δ 2.86 (s, 9H), 2.18 (s,
3H), 1.94 (s, 6H), 1.60 (d, J = 12.6 Hz, 3H), 1.53 (d, J = 11.8 Hz, 3H).
Embodiment 3
In 250 mL autoclaves, 26.2g is added（0.1 mol）1- iodos adamantane and 120 g ethyl acetate, toward above-mentioned solution
29.5g is passed through in middle 30min（0.5 mol）Front three amine gas, enclosed system, being heated at 90 DEG C reaction, to continue reaction 36 small
When；Reaction terminates, and reaction solution is cooled to room temperature, filtering, is washed to obtain white N, N, N- trimethyl -1- adamantyls with hexamethylene
Ammonium iodide 29.0g, yield 90.3%.
1H NMR (500 MHz, D2O) δ 2.84 (s, 9H), 2.16 (s,3H), 1.92 (s, 6H), 1.58
(d, J=12.5Hz, 3H), 1.52(d, J=12.5 Hz, 3H).
Embodiment 4
In 250 mL autoclaves, 21.5g is added（0.1 mol）1- bromos adamantane and 90 g hexamethylenes, into above-mentioned solution
17.7g is passed through in 30min（0.3 mol）Front three amine gas, enclosed system, it is heated to reaction at 90 DEG C and continues reaction 40 hours；
Reaction terminates, and reaction solution is cooled to room temperature, filtering, is washed to obtain white N, N, N- trimethyl -1- adamantyls with chloroform
Ammonium bromide 23.3g, yield 85.0%.
Embodiment 5
Weigh 57.4g（0.6 mol）Trimethylamine hydrochloride is added in the three-necked flask for filling 140g toluene, ice bath cooling（It is anti-
Only sodium hydroxide addition is too fast, and the heat of neutralization make it that solution temperature is too high and escapes trimethylamine）, stir lower addition sodium hydroxide alkali
Change to pH=10-11, be filtrated to get front three carbaryl liquid, obtained front three carbaryl liquid is poured into 250 mL autoclaves, and add
Enter 17.1g（0.1 mol）1- chloro adamantane, enclosed system, it is heated to reaction at 120 DEG C and continues reaction 24 hours.Reaction knot
Beam, reaction solution are cooled to room temperature, filtering, are washed to obtain white N, N, N- trimethyl -1- adamantyl ammonium chlorides with chloroform
20.05g yield 87.3%.
Embodiment 6
Weigh 76.5g（0.8 mol）Trimethylamine hydrochloride is added in the three-necked flask for filling 180 g dichloroethanes, and ice bath is cold
But（Prevent that sodium hydroxide addition is too fast, the heat of neutralization make it that solution temperature is too high and escapes trimethylamine）, stir lower addition hydrogen-oxygen
Change soda to pH=10-11, filtering.Obtained trimethylamine dichloroethanes liquid is poured into 250 mL autoclaves, and added
26.2g（0.1 mol）1- iodo adamantane, enclosed system, it is heated to reaction at 90 DEG C and continues reaction 24 hours.Reaction terminates,
Reaction solution is cooled to room temperature, filtering, is washed to obtain white N, N, N- trimethyl -1- adamantyl ammonium iodide 29.6g with acetone, receives
Rate 92.2%.
Embodiment 7
In 250 mL autoclaves, 10.8g is added（0.05 mol）1- bromos adamantane, 50 g dichloroethanes and 50g hexamethylenes,
Into above-mentioned solution 29.5g is passed through in 30min（0.5 mol）Front three amine gas, enclosed system, be heated at 100 DEG C reaction after
Continuous reaction 48 hours.Reaction terminates, and reaction solution is cooled to room temperature, filtering, is washed to obtain white N, N, N- front threes with chloroform
Base -1- adamantyl ammonium bromide 12.8g, yield 93.4%.
Claims (9)
- The synthetic method of 1.N, N, N- trimethyl -1- adamantyl ammonium halides, it is characterised in that comprise the following steps：1）In autoclave, 1- halos adamantane, trimethylamine and organic solvent are added by proportional quantity, is heated to 50 ~ 250 DEG C, it is close Close reaction 12 ~ 48 hours, obtain reaction solution；2）By step 1）Reaction solution be cooled to room temperature, be filtrated to get N, N, N- trimethyl -1- adamantyl ammonium halide crude products, use White sterling N, N, N- trimethyl -1- adamantyl ammonium halides are produced after organic solvent washing；Its synthetic route is as follows：。
- 2. N according to claim 1, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step Rapid 1）In trimethylamine feed postition have two kinds：Front three amine gas are passed through 1- halos adamantane and organic solvent mixed liquor by a In；Trimethylamine hydrochloride is first carried out quaternization and is filtrated to get trimethylamine by b in organic solvent with alkali hydroxide metal to be had Machine solution, add in 1- halo adamantane.
- 3. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that hydrogen It is sodium hydroxide or potassium hydroxide to aoxidize alkali metal.
- 4. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that have Solvent is any one or more mixture in C1 ~ C8 alcohol, ether, ester, alkane, aromatic hydrocarbons, halogenated hydrocarbons.
- 5. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that have Solvent is ethanol, isopropanol, methyl tertiary butyl ether(MTBE), 1,4- dioxane, ethyl acetate, n-hexane, hexamethylene, toluene, two Any one or more mixture in toluene, chloroform, dichloroethanes etc..
- 6. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that have Solvent is any one or more in isopropanol, 1,4- dioxane, ethyl acetate, hexamethylene, toluene, dichloroethanes etc. Mixture.
- 7. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step Rapid 1）In 1- halos adamantane and organic solvent mass ratio be 1:2.0~20, preferably 1:4.0~10.
- 8. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step Rapid 1）In 1- halos adamantane and the ratio between the amount for the material that feeds intake of trimethylamine be 1:1.2~20, preferably 1:2.0~ 10。
- 9. N according to claim 2, N, the synthetic method of N- trimethyl -1- adamantyl ammonium halides, it is characterised in that step Rapid 2）Any one or more mixture in ketone, ester, alkane and halogenated hydrocarbons that the organic solvent of middle washing is C1 ~ C8, it is excellent Any one or more elected as in acetone, butanone, ethyl acetate, n-hexane, hexamethylene, chloroform, dichloroethanes etc. is mixed Compound, more preferably acetone, ethyl acetate, hexamethylene or chloroform.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710964351.8A CN107721862B (en) | 2017-10-17 | 2017-10-17 | Synthesis method of N, N, N-trimethyl-1-adamantyl ammonium halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710964351.8A CN107721862B (en) | 2017-10-17 | 2017-10-17 | Synthesis method of N, N, N-trimethyl-1-adamantyl ammonium halide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107721862A true CN107721862A (en) | 2018-02-23 |
| CN107721862B CN107721862B (en) | 2020-04-07 |
Family
ID=61211376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710964351.8A Active CN107721862B (en) | 2017-10-17 | 2017-10-17 | Synthesis method of N, N, N-trimethyl-1-adamantyl ammonium halide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107721862B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699700A (en) * | 2019-10-30 | 2020-01-17 | 肯特催化材料股份有限公司 | Preparation method of adamantyl trimethyl ammonium hydroxide |
| CN113831277A (en) * | 2021-09-15 | 2021-12-24 | 宿迁时代储能科技有限公司 | Preparation method of hindered amine quaternary ammonium salt |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101648927A (en) * | 2009-09-01 | 2010-02-17 | 莫智龙 | Synthesis method of epoxypropyltrimethylammonium chloride |
| CN101935286A (en) * | 2009-06-26 | 2011-01-05 | 出光兴产株式会社 | Method for producing quaternary ammonium salt having adamantyl group |
| CN102344377A (en) * | 2011-08-02 | 2012-02-08 | 华南理工大学 | Method for synthesizing quaternary ammonium salt ionic liquid by microwave radiation heating |
-
2017
- 2017-10-17 CN CN201710964351.8A patent/CN107721862B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935286A (en) * | 2009-06-26 | 2011-01-05 | 出光兴产株式会社 | Method for producing quaternary ammonium salt having adamantyl group |
| CN101648927A (en) * | 2009-09-01 | 2010-02-17 | 莫智龙 | Synthesis method of epoxypropyltrimethylammonium chloride |
| CN102344377A (en) * | 2011-08-02 | 2012-02-08 | 华南理工大学 | Method for synthesizing quaternary ammonium salt ionic liquid by microwave radiation heating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699700A (en) * | 2019-10-30 | 2020-01-17 | 肯特催化材料股份有限公司 | Preparation method of adamantyl trimethyl ammonium hydroxide |
| CN110699700B (en) * | 2019-10-30 | 2020-06-30 | 肯特催化材料股份有限公司 | Preparation method of adamantyl trimethyl ammonium hydroxide |
| CN113831277A (en) * | 2021-09-15 | 2021-12-24 | 宿迁时代储能科技有限公司 | Preparation method of hindered amine quaternary ammonium salt |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107721862B (en) | 2020-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107721862A (en) | The synthetic method of the adamantyl ammonium halide of N, N, N trimethyl 1 | |
| CN104449647B (en) | Clean fracturing fluid complex thickener, fracturing fluid and preparation method thereof | |
| CN101565375A (en) | Adamantyl quaternary ammonium salt and preparation method thereof | |
| CN109535004B (en) | Preparation method of N, N, N-trimethyl-1-adamantyl ammonium hydroxide | |
| EA022826B1 (en) | Process for preparing an n,n-dialkylethanolamine having high colour stability | |
| CN112955430A (en) | Preparation method of brivaracetam and intermediate thereof | |
| CN101102996A (en) | Process for the preparation of 1-amino-3,5-dimethyladamantane hydrochloride | |
| CN106220511A (en) | A kind of preparation method of dimethyldiallylammonchloride chloride monomer | |
| JPH0237341B2 (en) | ||
| EP0908444B1 (en) | A process for producing a tertiary amine having high quality | |
| JP3502680B2 (en) | Method for producing quaternary ammonium salt | |
| CN102351755B (en) | Fluorine-containing imine cationic surfactant preparation method and application thereof | |
| US20150344385A1 (en) | Method for Producing Adamantane | |
| Zhao et al. | Synthesis and surface active properties of dimeric gemini sulfonate surfactants | |
| CN103664577B (en) | Preparation method of cinacalcet intermediate | |
| CA2043611A1 (en) | Continuous process for preparing quaternary ammonium salts | |
| TWI759615B (en) | A method for preparing 2-cyclohexyl cyclohexanol | |
| CN105384927B (en) | A kind of emulsion oil-in-water demulsifier and preparation method thereof | |
| JP4686197B2 (en) | Method for producing carboxylic acid amide, carboxylic acid amide derivative and method for producing the same | |
| CN104093697A (en) | Improved method for synthesising bis[3-(N,N-dialkylamino)propyl]ethers | |
| KR100211777B1 (en) | Process for producing aliphatic amine | |
| CN107573212A (en) | The synthetic method of trans 4 alkyl-cyclohexyl benzene structure liquid crystal intermediates and monomer | |
| EP0439249A1 (en) | Method for the synthesis of polyoxyalkylene tertiary amines | |
| CN106478423A (en) | Synthesis N, the method for N diisopropylethylamine | |
| CN101190888A (en) | Method for preparing 5-acetamido-2,4,6-triiodo-1,3-benzenedicarboxamides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |