CN102101820B - Isomerization method - Google Patents
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- CN102101820B CN102101820B CN201010593039.0A CN201010593039A CN102101820B CN 102101820 B CN102101820 B CN 102101820B CN 201010593039 A CN201010593039 A CN 201010593039A CN 102101820 B CN102101820 B CN 102101820B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/2226—Catalytic processes not covered by C07C5/23 - C07C5/31 with inorganic acids; with salt or anhydrides of acids
- C07C5/2233—Acids of sulfur; Salts thereof; Sulfur oxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to a method for preparing a trans-1,4-disubstituted cyclohexane compound with at least one benzene-derived residue at 1- or 4- position. The method comprises an isomerization step for converting one or a plurality of cis-configured cyclohexane ring to trans configuration in the presence of additional compound which forms carbocations while a strong acid is used.
Description
Technical field
The present invention relates to for the preparation of having at least one anti-form-1 derived from the residue of benzene in 1-or 4-position, the method of the dibasic compounds of 4-, the method comprises use strong acid and the cyclohexane ring of one or more cis-configuration is converted into the isomerization steps of transconfiguration under the existence of the compound of extra formation carbocation.
Background technology
Functional Chemicals is not only subject to the impact of functional group existing among them, but also is subject to the impact of their stereochemistry, i.e. their space structures with vital degree.A stereochemical important local domain is absorbed in the relative position of simple non-aromatic ring and these ring substituents.
A stereochemical basic problem is substituent cis/trans isomery on hexanaphthene.The isomery of the cyclohexane derivant of Isosorbide-5-Nitrae-replacement will be specifically discussed below.
Known reaction is the cis/trans isomerization of 4-alkyl-cyclohexyl benzene, the cyclohexane ring isomerization that wherein phenyl can be replaced by suitable measures, makes mainly to obtain Isosorbide-5-Nitrae-trans-isomer(ide) (JP 2004-256490A) by cis/trans mixture.Contrary with the present invention, isomerization occurs on the aromatic ring of electron rich.
So far, isomerization method have employed highly basic such as potassium tert.-butoxide or fluoride ion and has carried out (DE 102005034067A1).But, these isomerization methods in most cases with not satisfied productive rate, and/or due to less desirable side reaction generation itself be difficult to be separated product mixtures.Particularly produce product mixtures when fluorinated aromatic compounds, formed and polymerization or oligomeric subsequently because aryne may be there is in the basic conditions, or because the alkali fluorine position that attack replaces as nucleophilic reagent.
Finally, such as, George A.Olah, at " Superacid Chemistry " second edition Wiley, reviews the chemical property of the lower carbocation of strong acid (super acid) impact again in 2009.Also do not study the cis/trans stereochemical application of this chemical property for Isosorbide-5-Nitrae-substituted cyclohexane so far.
Summary of the invention
Have now been discovered a kind of universal method of the trans substituted cyclohexane compound for the preparation of formula I,
Wherein,
R
1represent unsubstituted, the straight chained alkyl with the highest 9 carbon atoms, or-CH (CH
3) CH
3,
R
2represent H, halogen, preferably F, have the alkyl of the highest 9 carbon atoms, there is the perfluoroalkyl of the highest 9 carbon atoms, or there is the perfluoro alkoxy of the highest 9 carbon atoms, also represent the alkoxyl group with the highest 9 carbon atoms for during s > 0
N represents 0,1 or 2,
M represents 1 or 2,
S represents 0,1 or 2,
P represents 1,2,3 or 4,
Q represents 0,1,2,3 or 4,
A
1represent anti-form-1,4-cyclohexylidene, and
Z
1expression-(CH
2)
t-, wherein t=0,1,2,3 or 4, preferably t=0,2 or 4,
Under the method is included in the existence of strong acid, preferably super acid and under the existence of the compound of extra formation carbocation, corresponding to the reaction of the Isosorbide-5-Nitrae-cis compounds of formula I.
Parent material used is formula II compound typically,
It has cis-configuration on cyclohexane ring, or comprises the mixture of the part with cis-configuration, wherein R
1, R
2, Z
1, m, n, p, q and s defined such as formula in I.
Form the compound of carbocation hereinafter referred to as catalyzer.Carbocation is formed by the reaction of catalyzer with acid.This catalyzer preferably uses with substoichiometric (sub-stoichiometric) amount, namely preferably adopts in based on the amount of 0.001 ~ 95mol% treating isomerized ground (substrate) in reality.The amount of particularly preferred added catalyzer is 0.01 ~ 10mol%.According to the preparation of parent material, under some situations, the interpolation of catalyzer is and nonessential, because there is the impurity playing catalyst action of sufficient amount.But, preferably add catalyzer separately.
Unique distinction according to method of the present invention is gentle program, trans content high in isomerization product and little by product.Added catalyzer can be separated without any problems.
Suitable strong acid mainly H
0those (super acids) that value is less than-11, preferred perfluorinated alkyl sulfonic acid, particularly trifluoromethanesulfonic acid, nine fluorine fourth sulfonic acid and derivatives thereof, such as three (three fluorosulfonyls) methane or (CF
3sO
2)
2nH.If desired, can by combining with Lewis acid the intensity strengthening acid further.If usage chain alkene is as catalyzer, this point can be particularly advantageous.Other super acid systems many (chapter 2 see in the Olah as above quoted, Superacid Chemistry) in the liquid phase of disclosing in pertinent literature as fluoro sulfuric acid, and and Lewis acid, as SbF
5in the mixture of (" evil spirit acid ").Usually particularly preferably non-oxide system, i.e. those of not sulfur acid, persulfuric acid or sulphur trioxide.This strong acid has carbocation-stability or super electrophilicity, and is conducive to the reaction of positively charged ion-promotion.Therefore, the strong acid in meaning of the present invention is the acid being suitable for producing with the compound forming carbocation carbocation.
In one preferred embodiment, the method is carried out under as the second month in a season of catalyzer or the existence of f-alkyl halides or sulfonate or the second month in a season or the tertiary alcohol.Used catalyst is preferably tertiary halogenide, the halogenide on the end of the bridge of the many rings of aliphatic hydrocarbon, or neopentyl halide compound.In this point, preferred halogenide is muriate, bromide and iodide, particularly muriate.Replace halogenide ground, under often kind of situation, hydroxyl is also possible.Catalyzer also can be the compound of many halos in pairs, such as haloform or four methyl halides.The example of good carbocation forming agent is the adamantane compound (preferred alcohols, halogenide or alkyl oxide) of bridgehead displacement, such as 1-adamantanol or 1-halo diamantane, also has norborneol and norcamphyl muriate in addition.Another substitutes is tertiary alkyl carboxylic acid, such as pivalyl chloride (2,2-dimethylpropionic acid chloride), because they form carbocation by eliminating CO after removing dechlorination root.Catalyzer suitable is in addition above-mentioned muriate or alcohol and the corresponding ether of other simple alcohols as methyl alcohol, such as methyl tertiary butyl ether.Due to good availability and efficiency, t butyl chloride (2-chloro-2-methyl propane) is used to be economical especially as catalyzer.
What be also suitable as catalyzer in principle is can form tertiary cationic alkene (such as 1-tetrahydrotoluene) by adding proton.
Catalyzer preferably uses with catalytic amount, uses especially with the amount being even less than the molar weight of added strong acid.The preferable amount of catalyzer is 0.01 ~ 10mol%, based on product meter, or 1 ~ 90mol%, preferably 5 ~ 20mol%, based on acid meter.
Add than pointed amount or even the more substantial catalyzer of stoichiometry may be disadvantageous in some cases for the method.
In practice, in for the raw material of the method, sometimes there is the impurity added corresponding to a kind of described catalyzer.In these cases, this kind of interpolation is unnecessary in some cases, if because particularly eliminate water subsequently and hydrogenation obtains parent material by the addition reaction of arylide on pimelinketone, then this parent material has comprised the material of the catalytic activity as impurity.
The method is preferably carried out in chlorination or fluorated solvent, such as methylene dichloride, 1,3-phenyl-difluoride, trifluoromethy benzene, 1,2,3,4-or 1,2,3,5-tetra-fluorobenzene, phenyl-pentafluoride or chlorination hydrofluoric ether.Suitable solvent is known (see G.A.Olah, div.publications) from super acid chemistry.
Temperature of reaction in the method preferably lower than 0 DEG C, more preferably less than-20 DEG C.Preferably temperature of reaction is 30 ~-180 DEG C, is particularly preferably 0 ~-100 DEG C and is very particularly preferably-30 ~-78 DEG C.Due to low technological temperature, produce little by product.Also susceptibility parent material can be adopted.
Although temperature of reaction is low, after the reaction times of 0.1 ~ 4 hour, usually obtain the product of expectation.
For being obtained by traditional method according to the isomerized hexanaphthene with cis-content for the treatment of in method of the present invention.Initial compounds through confirming is the pimelinketone that 4-replaces, such as 4-alkyl cyclohexanone, 4-(4-alkyl-cyclohexyl) pimelinketone, hexanaphthene-Isosorbide-5-Nitrae-diketone or corresponding acetal.There is the synthesis path through confirming being obtained hexanaphthene by these parent materials: the addition reaction on carbonyl of Grignard or lithium compound, carrying out subsequently eliminating and the hydrogenation of tetrahydrobenzene on standard catalyst.Each hydrogenation produces the cis/trans mixture that trans content is less than 85% (usually remarkable in this content) usually.Thus, the feature of a preferred method is, reaction product is each 1, configuration on the cyclohexane ring that 4-replaces corresponds to the transconfiguration of 95% or higher, wherein the configuration of parent material on the cyclohexane ring of at least one Isosorbide-5-Nitrae-replacement preferably corresponds to the transconfiguration of 90% or lower, preferably 85% or lower.Product preferably comprises the alltrans configuration of 97% or higher on Isosorbide-5-Nitrae-hexanaphthene residue.
According to a preferred method of the present invention extraly feature be also, as another processing step before the isomerization using acid according to the present invention, the method comprises cyclohexene ring, phenyl ring or cyclohexadiene ring hydrogen, and wherein this ring is converted into cyclohexane ring.Accurately, this ring is preferably converted into transconfiguration in isomerization, as long as it obtains from hydrogenation with cis-configuration.
A kind of for the isomerized effective ways of less desirable cis-content by Isosorbide-5-Nitrae-cyclohexane derivant according to method of the present invention.The method can be directly used in the trans content improving cis/trans mixture, even if trans-isomer(ide) ratio has been 85% or higher.Trans content after isomerization is preferably 95% or higher, is particularly preferably 97% or higher and especially 99% or higher.This content is based on rough (crude) mixture meter.The method may be used for the isomerization with the residue of the cis-content increased from trans-isomer(ide) enrichment process equally, such as, from the mother liquor of crystallisation process.Thus, can by isomerization reclaim not even can the residue of material of cis-configuration.
In the present invention one preferred embodiment, parameter n=1 in formula I, m=0, s=1 and Z
1for singly-bound.Preferably, q=1 or 2.R
1preferably there is linear alkyl or the sec.-propyl of 1 ~ 7 carbon atom, R
2be preferably F, linear alkyl or linear perfluoroalkyl or perfluoro alkoxy.
The terminal phenyl rings of formula I is preferably selected from the residue of following formula:
And particularly 3,5-difluorophenyls or 2,3-difluorophenyl.
Therefore, particularly preferred formula I product is
Or
Wherein preferred
Wherein R
2preferably represent H, F, alkyl, perfluoroalkyl or perfluoro alkoxy in each case a, be particularly preferably F or linear alkyl.
In order to remove by product, catalyst residue and low cis content, after single crystallisation step, usually obtain highly purified especially alltrans compound.If do not have effective isomerization method, generally for removing cis-isomeride needs multiple crystallisation step, and the cis-isomeride existed makes the crystallization of trans product more difficult.Therefore, productive rate is improved according to method of the present invention.
The subsequent disposal of the method and reaction mixture can be carried out with rhythmic reaction or with the program of successive reaction substantially.Successive reaction program comprises, such as, and the reaction in flow duct or in micro-reaction device.If desired, by select via the separation (such as extracting) between the filtration of solid-phase, chromatography, immiscible phase, the absorption on solid carrier, by distillation except desolventizing and/or azeotropic mixture, selectivity distillation, distillation, crystallization, cocrystallization or the nanofiltration on film, reaction mixture is processed.
In chart, ring
the cyclohexane ring of (having a little) expression Isosorbide-5-Nitrae-trans replacement and ring
represent the cyclohexane ring of the Isosorbide-5-Nitrae-replacement with mixing cis and transconfiguration or main cis-configuration.
Embodiment discloses other preferred process variable, the detailed content of embodiment---also carrying out concluding the content drawn according to general expertise---for being representative for the preferred implementation of method of the present invention and product thereof.
Embodiment
In order to measure cis/trans content and by-products content, study reaction product by means of HPLC.
Embodiment 1
20g parent material (64mmol, 44% cis on center ring) to be dissolved in 90g anhydrous methylene chloride (for what analyze) and to be cooled to-45 DEG C.2g trifluoromethanesulfonic acid (13mmol, 1.2ml) is added in this suspension.Drip the 0.15g 1-adamantanol (1.0mmol) in 9g methylene dichloride subsequently.This batch of material is stirred 1 ~ 3 hour again at-40 ~-45 DEG C, and period takes out sample every now and then for measuring isomerisation degree.When isomerization completes (the complete isomerization of sample after 1 ~ 2 hour), this batch of material is processed.
For process, 38ml water is added in this batch of material, is warming to about 20 DEG C subsequently.Isolate organic phase, with 22g citric acid three sodium solution (in water, 25%) and 2 × 20ml water washing, and be evaporated to drying in a rotary evaporator.Residue (20.2g) is contained in (takenup) heptane and also again evaporates.Crude product (light yellow crystal) has the cis/trans content of 0.7%, and trans desired by 98.3%, trans product content (HPLC).Except adamantane derivative, also there is another by product (in more detail it not being measured) with the similar residence time of 0.7%.
By being contained in heptane neutralization via the filtration of the 10g silica gel slurry in heptane, carry out purifying.Filtrate is evaporated (19.7g) in a rotary evaporator.Residue is dissolved in hot ethanol, and crystallization goes out colourless in fact, very pure alltrans product (16.2g, productive rate 81%, > 99.8%) at low temperatures.
Embodiment 2
168g parent material (525mmol, 59.3% cis on center ring) to be dissolved in 650ml anhydrous methylene chloride (for what analyze) and to be cooled to-40/-45 DEG C.9.5ml trifluoromethanesulfonic acid (108mmol) is added in this suspension.Drip the 1-adamantanol (8.3mmol) of the 1.26g in 50ml methylene dichloride subsequently.This batch of material is stirred 1 ~ 2 hour again at-40 ~-45 DEG C, and period takes out sample every now and then for measuring isomerisation degree.When isomerization completes (the complete isomerization of sample after 30 minutes), this batch of material is processed.
For process, the mixture of 25% hydrochloric acid of the ice of 175g and 350ml is added in this batch of material, is warming to about 20 DEG C subsequently.Isolate organic phase, with 175ml sodium hydrogen carbonate solution (in water, 5%) and 175ml water washing, and be evaporated to drying in a rotary evaporator.Residue (168.8g) is contained in heptane.Crude product (light yellow crystal) has the cis/trans product of 0.23%, and the trans/trans product assay (GC) of the expectation of 99.7%.
By being contained in the heptane neutralization of 300ml via the filtration of the silica gel slurry in heptane, carry out purifying.Filtrate is evaporated (161.7g) in a rotary evaporator.Residue is dissolved in hot ethanol, and crystallization goes out colourless in fact, very pure alltrans product (145.7g, productive rate 86.7%, > 99.9%) at low temperatures.
Embodiment 3
Repeat embodiment 1, catalyzer 1-adamantanol is changed to the 2-chloro-2-methyl propane of equivalent simultaneously.
Crude product (light yellow crystal) has 1.1% cis/trans product assay, and the trans/trans product assay (HPLC) desired by 97.9%.
Other combination of embodiment of the present invention and distortion can be obtained in Accessory Right claim.
Claims (9)
1. for the preparation of the method for the compounds of the Isosorbide-5-Nitrae-trans-replacement of formula I,
Wherein,
R
1represent unsubstituted, the straight chained alkyl with the highest 9 carbon atoms, or-CH (CH
3) CH
3,
R
2represent H, halogen, has the alkyl of the highest 9 carbon atoms, has the perfluoroalkyl of the highest 9 carbon atoms, or has the perfluoro alkoxy of the highest 9 carbon atoms, also represents the alkoxyl group with the highest 9 carbon atoms for during s > 0,
M represents 1 or 2,
N represents 0,1 or 2,
P represents 1,2,3 or 4,
Q represents 0,1,2,3 or 4,
S represents 0,1 or 2,
A
1represent anti-form-1,4-cyclohexylidene, and
Z
1expression-(CH independently under often kind of situation
2)
t-, wherein t=0,1,2,3 or 4,
The method is included in H
0under value is less than the strong acid existence of-11 and under the existence of the compound of extra formation carbocation, corresponding to the reaction of the Isosorbide-5-Nitrae-cis compounds of formula I.
2. the method for claim 1, is characterized in that, the method is carried out under the existence of perfluoro alkyl sulfonic acid.
3. the method for claim 1 or 2, is characterized in that, this reaction is carried out under one or more are with uncle or the alkyl oxide of secondary alkyl halide or sulfonate, uncle or secondary alcohol or these alcohol or the additive existence of alkanoates form.
4. the method for claim 1 or 2, is characterized in that, the trans/trans-bis cyclohexane compound of preparation formula IA,
Wherein m, p, q, s, R
1and R
2as defined in claim 1.
5. the method for claim 1 or 2, is characterized in that, the compound of described formula I is the compound of formula I-1,
Wherein m, s, R
1, R
2, A
1, Z
1as defined in claim 1.
6. the method for claim 1 or 2, is characterized in that, this reaction is carried out being less than or equal at the temperature of 0 DEG C.
7. the method for claim 1 or 2, is characterized in that, this reaction is carried out in as the chlorination of solvent and/or fluorinated hydrocarbons.
8. the method for claim 1 or 2, is characterized in that, the configuration of reaction product on the cyclohexane ring of each Isosorbide-5-Nitrae-replacement corresponds to the transconfiguration of 95% or higher.
9. the method for claim 1 or 2, is characterized in that, as another processing step before the isomerization of the formula of acquisition I, the method is included in phenyl ring, cyclohexene ring or cyclohexadiene ring hydrogen, and wherein this ring is converted into the cyclohexane ring of Isosorbide-5-Nitrae-replacement.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102009058574.5 | 2009-12-17 | ||
| DE102009058574.5A DE102009058574B4 (en) | 2009-12-17 | 2009-12-17 | Method for isomerization |
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|---|---|
| CN102101820A CN102101820A (en) | 2011-06-22 |
| CN102101820B true CN102101820B (en) | 2015-01-14 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2532641B1 (en) * | 2011-06-07 | 2015-08-19 | Merck Patent GmbH | Isomerisation method |
| JP2014162752A (en) * | 2013-02-25 | 2014-09-08 | Dic Corp | Compound, liquid crystal composition, and display device |
| WO2018151188A1 (en) * | 2017-02-20 | 2018-08-23 | Jnc株式会社 | Method for producing trans-1,4-disubstituted cyclohexane derivatives |
| CN108277019A (en) * | 2017-11-13 | 2018-07-13 | 晶美晟光电材料（南京）有限公司 | A kind of preparation method of trans cvclohexvl base class liquid-crystal compounds |
| CN110964538B (en) * | 2019-12-18 | 2022-01-04 | 江苏创拓新材料有限公司 | Transposition method of 1-cyclohexyl-2, 3-difluorobenzene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304914A (en) * | 2000-10-02 | 2001-07-25 | 烟台万润精细化工有限责任公司 | Transform process for cis (or trans)-isomer of alkyl cyclohexyl benzene derivative |
| CN1911888A (en) * | 2005-08-12 | 2007-02-14 | 石家庄永生华清液晶有限公司 | 2,3,2,'3' tetrafluoro diphenyl acetylene derivative, its composition, preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004256490A (en) * | 2003-02-27 | 2004-09-16 | Nagase Chemtex Corp | Method for producing trans-cyclohexane derivative |
| DE102005034067A1 (en) | 2004-08-13 | 2006-02-23 | Merck Patent Gmbh | Preparation of six membered organic compound (in trans form), useful as content materials of e.g. mesogen compounds, comprises conversion of corresponding organic compound (in cis form) with fluoride-containing compounds |
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- 2009-12-17 DE DE102009058574.5A patent/DE102009058574B4/en active Active
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304914A (en) * | 2000-10-02 | 2001-07-25 | 烟台万润精细化工有限责任公司 | Transform process for cis (or trans)-isomer of alkyl cyclohexyl benzene derivative |
| CN1911888A (en) * | 2005-08-12 | 2007-02-14 | 石家庄永生华清液晶有限公司 | 2,3,2,'3' tetrafluoro diphenyl acetylene derivative, its composition, preparation method and use |
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| DE102009058574B4 (en) | 2017-08-31 |
| DE102009058574A1 (en) | 2011-06-22 |
| CN102101820A (en) | 2011-06-22 |
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