CN107759445A - One kind prepares 1（3,3, Dimethylcyclohexyl）The method of ethanol - Google Patents
One kind prepares 1（3,3, Dimethylcyclohexyl）The method of ethanol Download PDFInfo
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- CN107759445A CN107759445A CN201711181881.1A CN201711181881A CN107759445A CN 107759445 A CN107759445 A CN 107759445A CN 201711181881 A CN201711181881 A CN 201711181881A CN 107759445 A CN107759445 A CN 107759445A
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- China
- Prior art keywords
- formula
- preparation
- acid
- dimethylcyclohexyl
- reaction
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The present invention relates to technical field of organic synthesis, and in particular to the method that one kind prepares 1 (3,3, Dimethylcyclohexyl) ethanol.The preparation method is that the compound shown in formula (II) is hydrolyzed into reaction, is produced.The method described in the present invention reagent is easy to get, and cost is cheap, simple to operate, nuisanceless to environment, is more suitable for large-scale industrial production.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to one kind prepares 1- (3,3 ,-Dimethylcyclohexyl) ethanol
Method.
Background technology
Spices sea Buddhist Moschus is prepared by following reaction：
During formula (III) is prepared, following side reaction occurs：
After the reaction of preparation formula (III) terminates, formula (III) is separated by rectifying mode；Residual remaining kettle is formula (II)
Mixture, and formula (II) is unwanted accessory substance, if do not reclaimed, can cause the waste of material, increases cost, while also can
Pressure is brought to environmental protection.
Therefore, in this context, its recovery method is improved to be very important.
The content of the invention
The present invention provides the side that one kind prepares 1- (3,3 ,-Dimethylcyclohexyl) ethanol (compound i.e. shown in formula (I))
Method, this method include, and the compound shown in formula (II) is hydrolyzed into reaction, produced.
Preferably, the hydrolysis is carried out in the presence of a mineral acid；It is further preferred that the inorganic acid is salt
One kind in acid, sulfuric acid, hydrobromic acid or phosphoric acid, using sulfuric acid to be optimal.
It is to be swift in response using the advantages of above-mentioned inorganic acid, without other accessory substances, reaction conversion is complete, and acid used
It can repeat to apply mechanically, reduce the harm to environment.Preferably, the inorganic acid and the mol ratio of the compound shown in formula (II)
For 1-10:1, more preferably 1-3:1.Advantage is to be swift in response, and inorganic acid used can be applied mechanically more than 4 times, when inorganic acid mistake
It when more, can cause to waste, and have partial impurities generation.When inorganic acid is not enough measured, it is incomplete that progress can be reacted.
After hydrolysis terminates, water layer is removed by being layered, is then simply distilled, it is possible to obtain high-purity
Compound shown in formula (I).And water layer can repeat to apply mechanically, tail gas absorption part can also apply mechanically.
Preferably, the temperature of the hydrolysis is 30 DEG C -100 DEG C；It is further preferred that the temperature is 80 DEG C -100
DEG C, when temperature is in this scope, the conversion ratio of reaction greatly promotes, and can reach more than 98%.
Reacted in said temperature, can effectively ensure the performance level of reaction, and do not produce unwanted pair
Product, reaction speed is fast, and 1- (3,3 ,-Dimethylcyclohexyl) ethanol fragrance of preparation is pure, comment fragrant effect and existing sample without
Difference.
Preferably, the compound shown in the formula (II) is the accessory substance of following reaction.
Further, compound shown in formula (III) is prepared by raw material of compound shown in formula (I) the invention provides one kind
Method,
Step includes：
With formula (I) for raw material, reacted with methyloxetane, generate formula (III) compound, obtain reaction system, its
Middle formula (II) compound is the accessory substance in reaction；
Characterized in that, formula (III) is separated from the reaction system, take remaining system that reaction is hydrolyzed, produce formula
(I) compound.
The method described in the present invention reagent is easy to get, and cost is cheap, simple to operate, nuisanceless to environment, is more suitable for advising greatly
The industrialized production of mould, the recycling that can ensure material in the extra large Buddhist Moschus product of preparation is applied, it is cost-effective, no
New impurity can be introduced, adding reagent can apply mechanically.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
The amount of reactant and product is measured by gas-chromatography (Agilent GC 6890) in following examples.Following reality
Apply in example, the conversion ratio and selectivity of reaction are calculated by below equation：
Conversion ratio=(the feed molar amount remained in raw material input mole-product)/raw material input mole × 100%
Theoretical molar amount × 100% of actual molar quantity/target product of selectivity=target product
The source of following examples Chinese style (II) mixture is：
At room temperature, by compound, 2mol methyloxetane and 200mL dichloromethane shown in 1mol formula (I)
Add in 1000 milliliters of flask, after stirring, reduce reaction temperature to -78 DEG C.Then, 2mol boron trifluoride is added,
Low temperature 1h, through reaction is quenched, separating compound shown in the formula (III) in reaction system (can be further used for preparing sea
Buddhist Moschus), residue is formula (II) mixture.
Embodiment 1
The present embodiment provides a kind of preparation method of the compound shown in formula (I), as follows：
20g formulas (II) mixture is added in 100ml four-hole bottles, the aqueous sulfuric acids of 14g 50%, is started to warm up to 80 DEG C, instead
Answer 2 hours, be layered, rectifying obtains target product.
The conversion ratio that control measures reaction in gas phase is 99%, and selectivity is 98%.
Embodiment 2
The present embodiment provides a kind of preparation method of the compound shown in formula (I), as follows：
20g formulas (II) mixture, 14g 6mol/L aqueous hydrochloric acid solutions, connection tail gas absorption dress are added in 100ml four-hole bottles
Put and (tail gas absorption is done with water), start to warm up to 80 DEG C, react 5 hours, layering, organic phase rectifying obtains target product formula (I).
The conversion ratio that control measures reaction in gas phase is 99%, and selectivity is 96%.
Embodiment 3
The present embodiment provides a kind of preparation method of the compound shown in formula (I), as follows：
20g formulas (II) mixture is added in 100ml four-hole bottles, 20g 6mol/L hydrobromic acid aqueous solutions, connects tail gas absorption
Device (does tail gas absorption) with water, starts to warm up to 80 DEG C, reacts 3 hours, and layering, rectifying obtains target product.
The conversion ratio that control measures reaction in gas phase is 99%, and selectivity is 97%.
Embodiment 4
The present embodiment provides a kind of preparation method of the compound shown in formula (I), as follows：
20g formulas (II) mixture is added in 100ml four-hole bottles, the phosphate aqueous solutions of 15g 50%, is started to warm up to 80 DEG C, instead
Answer 2 hours, be layered, rectifying obtains target product.
The conversion ratio that control measures reaction in gas phase is 99%, and selectivity is 95%.
Embodiment 5
The present embodiment provides a kind of preparation method of the compound shown in formula (I), with differing only in sulphur for embodiment 1
Acid replaces with aqueous phase after embodiment 1 is layered.
The conversion ratio that control measures reaction in gas phase is 98%, and selectivity is 98%.
Embodiment 6
The present embodiment provides a kind of preparation method of the compound shown in formula (I), with differing only in sulphur for embodiment 1
Acid replaces with aqueous phase after embodiment 5 is layered.
The conversion ratio that control measures reaction in gas phase is 98%, and selectivity is 96%.
Embodiment 7
The present embodiment provides a kind of preparation method of the compound shown in formula (I), with differing only in sulphur for embodiment 1
Acid replaces with aqueous phase after embodiment 6 is layered.
The conversion ratio that control measures reaction in gas phase is 98%, and selectivity is 96%.
Embodiment 8
The present embodiment provides a kind of preparation method of the compound shown in formula (I), with differing only in sulphur for embodiment 1
Acid replaces with aqueous phase after embodiment 7 is layered.
The conversion ratio that control measures reaction in gas phase is 98%, and selectivity is 96%.
Embodiment 9
The present embodiment provides a kind of preparation method of the compound shown in formula (I), and heating is differed only in embodiment 1
To 30 DEG C, react 5 hours
The conversion ratio that control measures reaction in gas phase is 56%, and selectivity is 99%.
Embodiment 10
The present embodiment provides a kind of from the reaction for preparing extra large Buddhist Moschus for raw material with formula (I), the method for reclaiming accessory substance, its
Step is as follows：Fetch 1- (3, the 3 ,-Dimethylcyclohexyl) ethanol (being made by embodiment 1) for receiving 1mol, 2mol methyl epoxy
Propane and 200mL dichloromethane are added in 1000 milliliters of flask, after stirring, reduce reaction temperature to -78 DEG C.So
Afterwards, 2mol boron trifluoride is added, reaction is quenched in low temperature 1h, and rectifying must both produce compound shown in formula (III).(formula
(III) compound shown in can further prepare extra large Buddhist Moschus：Pyridine does acid binding agent and product sea Buddhist Moschus is made with propionyl chloride reaction,
Product purity 99%, removes to comment perfume (or spice), and fragrance is consistent with the product of in the market.)
Compound shown in formula (III) is separated from the system, remaining system 20g is taken, adds 14g50% aqueous sulfuric acids,
80 DEG C are warming up to, is reacted 2 hours, layering, rectifying obtains compound shown in formula (I).
The conversion ratio that control measures reaction in gas phase is 99%, and selectivity is 98%.
Although above the present invention is made to retouch in detail with general explanation, embodiment and experiment
State, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, are belonged to claimed
Scope.
Claims (9)
1. the method that one kind prepares 1- (3,3 ,-Dimethylcyclohexyl) ethanol, it is characterised in that compound passes through as shown in formula (II)
Hydrolysis is made,
2. it is the method that raw material prepares compound shown in formula (III) with 1- (3,3 ,-Dimethylcyclohexyl) ethanol,
Methods described, for raw material, is reacted with 1- (3,3 ,-Dimethylcyclohexyl) ethanol shown in Formulas I with methyloxetane
Generate compound shown in formula (III)；
Characterized in that, after the reaction to be terminated to compound separation shown in the formula (III) in rear gained reaction system, residue
1- (3,3 ,-Dimethylcyclohexyl) ethanol is made through hydrolyzing.
3. preparation method according to claim 1 or 2, it is characterised in that the hydrolysis is in the presence of a mineral acid
Carry out.
4. preparation method according to claim 3, it is characterised in that the inorganic acid is hydrochloric acid, sulfuric acid, hydrobromic acid or phosphorus
One kind in acid.
5. the preparation method according to claim 3 or 4, it is characterised in that the inorganic acid and the chemical combination shown in formula (II)
The mol ratio of thing is 1-10:1.
6. according to the preparation method described in claim any one of 3-5, it is characterised in that shown in the inorganic acid and formula (II)
The mol ratio of compound is 1-3:1.
7. according to the preparation method described in claim any one of 1-6, it is characterised in that the temperature of the hydrolysis is 30
℃-100℃。
8. preparation method according to claim 7, it is characterised in that the temperature is 80 DEG C -100 DEG C.
9. according to the preparation method described in claim any one of 1-8, it is characterised in that the hydrolysis uses sulfuric acid, and hydrolysis is instead
The temperature answered is 80 DEG C -100 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711181881.1A CN107759445A (en) | 2017-11-23 | 2017-11-23 | One kind prepares 1（3,3, Dimethylcyclohexyl）The method of ethanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711181881.1A CN107759445A (en) | 2017-11-23 | 2017-11-23 | One kind prepares 1（3,3, Dimethylcyclohexyl）The method of ethanol |
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|---|---|
| CN107759445A true CN107759445A (en) | 2018-03-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711181881.1A Pending CN107759445A (en) | 2017-11-23 | 2017-11-23 | One kind prepares 1（3,3, Dimethylcyclohexyl）The method of ethanol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024003271A1 (en) * | 2022-06-30 | 2024-01-04 | Firmenich Sa | Process for preparation of ether, thioether or secondary amine derivatives in the presence of a heterogeneous acidic catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166412A (en) * | 1990-08-28 | 1992-11-24 | Firmenich S.A. | Esters and their use in perfumery |
| CN1512980A (en) * | 2001-06-01 | 2004-07-14 | ����µ��ɷ�����˾ | Cycloalkanecarboxylic acid derivatives as fragrants with musk characteristics |
| CN101066911A (en) * | 2007-06-18 | 2007-11-07 | 浙江普洛医药科技有限公司 | Process of preparing beta-p-hydroxyphenyl ethanol |
| WO2009034510A2 (en) * | 2007-09-11 | 2009-03-19 | Firmenich Sa | Selective preparation of some 2-alkoxy-ethanol derivatives |
-
2017
- 2017-11-23 CN CN201711181881.1A patent/CN107759445A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166412A (en) * | 1990-08-28 | 1992-11-24 | Firmenich S.A. | Esters and their use in perfumery |
| CN1512980A (en) * | 2001-06-01 | 2004-07-14 | ����µ��ɷ�����˾ | Cycloalkanecarboxylic acid derivatives as fragrants with musk characteristics |
| CN101066911A (en) * | 2007-06-18 | 2007-11-07 | 浙江普洛医药科技有限公司 | Process of preparing beta-p-hydroxyphenyl ethanol |
| WO2009034510A2 (en) * | 2007-09-11 | 2009-03-19 | Firmenich Sa | Selective preparation of some 2-alkoxy-ethanol derivatives |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024003271A1 (en) * | 2022-06-30 | 2024-01-04 | Firmenich Sa | Process for preparation of ether, thioether or secondary amine derivatives in the presence of a heterogeneous acidic catalyst |
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Address after: 102206 6th floor, building 4, hospital 9, medical Road, Life Science Park, Changping District, Beijing Applicant after: Purpana (Beijing) Technologies Co.,Ltd. Address before: 102206, No. 9, building 4, 4 Life Garden Road, Changping District science and Technology Park, Beijing, 401 Applicant before: Purpana (Beijing) Technologies Co.,Ltd. |
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Application publication date: 20180306 |
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