CN103787936B - A kind of industrialized production is with the trans simple synthesis to first sulfydryl cinnamyl alcohol - Google Patents
A kind of industrialized production is with the trans simple synthesis to first sulfydryl cinnamyl alcohol Download PDFInfo
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Abstract
The present invention relates to the trans simple synthesis to first sulfydryl cinnamyl alcohol of a kind of industrialized production. The method includes: thioanisole and formylation reagent carry out formylation reaction to be prepared first sulfydryl benzaldehyde; First sulfydryl benzaldehyde and acetaldehyde condensation under catalyst action are prepared trans to first sulfydryl cinnamic aldehyde, then, trans first sulfydryl cinnamic aldehyde is obtained trans to first sulfydryl cinnamyl alcohol through reduction. The method raw material of the present invention is cheap and easy to get, and reaction condition is easily operated, and reaction selectivity is high, and product cost is low, safe and environment-friendly, is suitable to industrialized production.
Description
Technical field
The present invention relates to a kind of for the trans synthetic method to first sulfydryl cinnamyl alcohol of industrialized production, belong to field of pharmaceutical chemistry technology.
Background technology
Trans is the synthesis of trans critical materials to methylsulfonyl cinnamyl alcohol to first sulfydryl cinnamyl alcohol, and the latter is the key intermediate of the medicines such as synthetic antibiotic thiamphenicol and Florfenicol. Trans to first sulfydryl cinnamyl alcohol structural formula such as shown in formula I:
United States Patent (USP) 5352832 and Oida et al. are (referring to Chem.Pharm.Bull.2000,48,6940) synthetic method of trans-p-methylsulfonyl cinnamyl alcohol is disclosed respectively, be all with to methylsulfonyl phthaladehyde for initial feed, but the cost of material height used in its synthesis, severe reaction conditions, some raw material are also inflammable and explosive, it is unfavorable for the drawback of industrialized production
Chinese patent document CN101921214A provides the synthetic method of a kind of trans-p-methylsulfonyl cinnamyl alcohol, with 4-chloro-benzaldehyde for initiation material, through replacing preparation to first sulfydryl benzaldehyde with sodium methyl mercaptide, then 1-(4-first mercaptophenyl is prepared with Grignard reagent vinyl halide for magnesium)-2-propenyl, then under acid catalysis, rearrangement obtains trans to first sulfydryl cinnamyl alcohol, prepares trans-p-methylsulfonyl cinnamyl alcohol then through oxidation. In the method, trans that through peroxidating prepared by first sulfydryl cinnamyl alcohol trans-p-methylsulfonyl cinnamyl alcohol is reasonable in design in final step, and reaction yield is high. But the deficiency of method is in that: replace in reaction and the last handling process of 4-chloro-benzaldehyde at sodium methyl mercaptide, it is difficult to controlling the generation of special smell methanthiol, the generation of special smell methanthiol is unfavorable for environmental conservation. In grignard reaction thereafter, the vinyl halide that price is high will being used for magnesium or unworkable bromine ethylene, and this reaction to carry out in ether solvent, anhydrous and oxygen-free when, safe operation process hidden danger is high, is unfavorable for industrializing implementation.Rearrangement process easily produces the polymer caused by carbonium ion, is unfavorable for the purification of final products.
Summary of the invention
Synthesizing the deficiencies in the prior art for trans-p-methylsulfonyl cinnamyl alcohol, the present invention provides a kind of environmental protection, the trans synthetic method to first sulfydryl cinnamyl alcohol of simple and direct industrialized production, and the preparation for thiamphenicol antibiotics medicine provides key intermediate basis.
Technical scheme is as follows:
A kind of industrialized production, with the trans simple synthesis to first sulfydryl cinnamyl alcohol, with thioanisole for initial feed, comprises the following steps that
(1) thioanisole and formylation reagent carry out formylation reaction in organic solvent I, prepare sulfydryl benzaldehyde;
Described formylation reagent is N,N-dimethylformamide and any one the combination of phosphorus oxychloride, solid phosgene, oxalyl chloride or two phosgene;
Described organic solvent I is selected from the one in N,N-dimethylformamide, dichloromethane, chloroform, 1,2-dichloroethanes, oxolane or its mixing;
(2) under base catalyst exists, sulfydryl benzaldehyde and acetaldehyde are carried out aldol reaction in organic solvent II, prepare trans to sulfydryl cinnamic aldehyde;
Described base catalyst is one of sodium hydroxide, potassium hydroxide, potassium acetate, potassium carbonate, potassium bicarbonate, potassium fluoride, TBAH or combination;
Described organic solvent II is oxolane, methanol, ethanol, isopropanol or n-butyl alcohol;
(3) in the presence of a reducing agent, by trans to sulfydryl cinnamic aldehyde in organic solvent II, carry out reduction reaction, obtain trans to sulfydryl cinnamyl alcohol;
Described reducing agent is sodium borohydride, potassium borohydride or sodium cyanoborohydride;
Step (3) described organic solvent II is identical with organic solvent II in step (2).
According to the invention it is preferred to:
In step (1), described formylation reagent is DMF and phosphorus oxychloride mol ratio (1.0-5): the combination of 1, or DMF and solid phosgene mol ratio (3.0-9.0): the combination of 1.
In step (1), described organic solvent I is preferably DMF or 1,2-dichloroethanes. When organic solvent I selects DMF, it not only makes organic solvent but also make formylation reagent.
In step (1), described organic solvent I and the mass ratio of thioanisole are (0.8-3.5): 1.
In step (1), described thioanisole is 1:1.0��1.8 with the mol ratio of phosphorus oxychloride, solid phosgene, oxalyl chloride or two phosgene in formylation reagent;
In step (1); described formylation reaction is undertaken by with the next stage: under subzero 10 DEG C of conditions; phosphorus oxychloride in formylation reagent, solid phosgene, oxalyl chloride or two phosgene are added drop-wise to thioanisole, N; in dinethylformamide and organic solvent I; then; react 1-3 hour at 0 DEG C, then be warming up to 20 DEG C of reactions 1-3 hour, then heat to 60-70 DEG C and react 1-3 hour.
In step (2), described acetaldehyde is acetaldehyde solution or the Metaldehyde of mass ratio 40��50%. It is preferred that, the degree of polymerization of described Metaldehyde is 3-20. Preferred Metaldehyde degree of polymerization 8-15.
In step (2), the described mol ratio to first sulfydryl benzaldehyde Yu acetaldehyde is 1:1.0-2.0. Metaldehyde amounts to into free aldehyde meter.
In step (2), reaction temperature is 0 DEG C of reflux temperature to organic solvent II.
In step (3), the described trans mol ratio to sulfydryl cinnamic aldehyde and reducing agent is 1:0.25-0.5, and reaction temperature is 0 DEG C of reflux temperature to organic solvent II.
The method of the present invention, with thioanisole for initiation material, reaction scheme is as follows:
In the inventive method, it does not have limit in detail, all by state of the art. Such as, the post processing such as the separation of the product of each step, washing, solvent recovery all can refer to prior art and operates routinely. Embodiment will be described in more detail. The method that following post processing is provided at this:
1, step (1) product postprocessing: after reaction terminates, it is cooled to 20 DEG C, by reaction liquid down in frozen water, regulating pH value with sodium hydrate aqueous solution is 6-7, and extraction into ethyl acetate 2-3 time merges organic facies, saturated sodium-chloride washs, layering, anhydrous sodium sulfate dries organic facies, obtains first sulfydryl benzaldehyde after precipitation; Weak yellow liquid.
2, step (2) product postprocessing: after reaction terminates, regulating pH value with dilute hydrochloric acid is 6-6.5, and extraction into ethyl acetate 2-3 time merges organic facies, and saturated sodium-chloride washs, layering, and anhydrous sodium sulfate dries organic facies, obtains trans to sulfydryl cinnamic aldehyde after precipitation; Weak yellow liquid.
3, step (3) product postprocessing: after reaction terminates, decompression and solvent recovery, then adding water, regulating pH value with dilute hydrochloric acid is 7, extraction into ethyl acetate 2-3 time, merge organic facies, saturated sodium-chloride washs, layering, and anhydrous sodium sulfate dries organic facies, after precipitation, obtain trans to first sulfydryl cinnamyl alcohol (I) by 50% recrystallizing methanol; White powdery solids.
The technical characterstic of the present invention and excellent results:
The method of the present invention is thioanisole is raw material, prepares trans to sulfydryl cinnamyl alcohol through formylated, aldol condensation, reduction. Thioanisole and formylation reagent are first reacted and generate sulfydryl benzaldehyde by the method for the present invention; then generate trans to sulfydryl cinnamic aldehyde with acetaldehyde generation aldol reaction under catalyst action, hereafter utilize a small amount of reducing agent reduction aldehyde radical to prepare trans to sulfydryl cinnamyl alcohol. Raw material of the present invention is cheap and easy to get, and reaction condition is easily operated, successfully avoids use sodium methyl mercaptide, grignard reagent and inflammable and explosive solvent, lays a good foundation for safe and environment-friendly industrialized production.
The method of the present invention, the product purity of each step is all in 98-99.9%, end-product purity more than 99.6%, and yield is up to 96%; Reaction selectivity is high, and product cost is low, is suitable to industrialization large-scale production.
Accompanying drawing explanation
Fig. 1 is the trans liquid chromatogram to first sulfydryl cinnamyl alcohol that embodiment 6 obtains.
Detailed description of the invention
Embodiments discussed below describes the present invention in detail, but the present invention is not limited only to following example. Benzene feedstock methyl sulfide, market is commercially available. First sulfydryl benzaldehyde, the trans purity to first sulfydryl cinnamic aldehyde by gas chromatographic detection, are denoted as (GC) by gained intermediate product; The trans purity to first sulfydryl cinnamyl alcohol of finished product is detected by high performance liquid chromatography, is denoted as (HPLC).
Using dilute hydrochloric acid concentration to be about 10% mass ratio in embodiment, other use the concentration % of solvent to be mass percent.
One, the preparation to first sulfydryl benzaldehyde (II)
Embodiment 1: the preparation to first sulfydryl benzaldehyde
The four-hole boiling flask of the 500mL equipped with stirring, thermometer, reflux condensate device and addition funnel adds thioanisole 124.0 grams (1.0 moles), N, dinethylformamide 200 grams, it is cooled to subzero 10 DEG C, being slowly added dropwise 161.1 grams of (1.05 moles) phosphorus oxychloride, drip and finish, 0 DEG C is reacted 2 hours, naturally rise to 20 DEG C to react 2 hours, then rise to 60-70 DEG C and react 2 hours.Reaction terminates.
It is cooled to 20 DEG C, by reaction liquid down in 1500 grams of mixture of ice and water, regulating pH value with 40% sodium hydrate aqueous solution is 6-7, three (250g �� 3 of extraction into ethyl acetate, share 750 grams), merge organic facies, 200 grams of saturated sodium-chloride washings, layering, 40 grams of dry organic faciess of anhydrous sodium sulfate, the weak yellow liquid 144.5 grams to first sulfydryl benzaldehyde, gas phase purity 99.3%, yield 95.0% is obtained after precipitation.
Embodiment 2: the preparation to first sulfydryl benzaldehyde (II)
The four-hole boiling flask of the 500mL equipped with stirring, thermometer, reflux condensate device and addition funnel adds thioanisole 124.0 grams (1.0 moles), N, dinethylformamide 100 grams, it is cooled to-10 DEG C, is slowly added dropwise the solution containing 109 grams of (1.1 moles) solid phosgenes and 300 gram of 1,2-dichloroethanes, drip and finish, 0 DEG C is reacted 2 hours, naturally rises to room temperature (20 DEG C) and reacts 2 hours, then rises to 60-70 DEG C and reacts 2 hours. Reaction terminates, and is cooled to 20 DEG C, by reaction liquid down in 1500 grams of mixture of ice and water, regulating pH value with 40% sodium hydrate aqueous solution is that 6-7,1,2-dichloroethanes extracts three (200g �� 3, share 600 grams), merge organic facies, 200 grams of saturated sodium-chloride washings, layering, anhydrous sodium sulfate (40 grams) dries organic facies, obtain after precipitation first sulfydryl benzaldehyde weak yellow liquid 145.9 grams, gas phase purity 99.7%, yield 96.1%.
Two, the trans preparation to sulfydryl cinnamic aldehyde (III)
Embodiment 3: the trans preparation to sulfydryl cinnamic aldehyde
The four-hole boiling flask of the 1000mL equipped with stirring, thermometer and addition funnel adds 300 grams of water, 10.0 gram potassium acetate, it is warming up to 30 DEG C, drips 76.0 grams (0.5 moles) mixed solution to sulfydryl benzaldehyde, 66 gram of 40% acetaldehyde solution and 200 grams of methanol, within about 3 hours, finish. Hereafter react 2 hours in 30 DEG C. Regulating pH value with dilute hydrochloric acid is 6, extraction into ethyl acetate three times (sharing 450 grams), merge organic facies, 200 grams of saturated sodium-chloride washings, layering, anhydrous sodium sulfate (30 grams) dries organic facies, weak yellow liquid 82.8 grams is obtained after precipitation, obtain trans to sulfydryl cinnamic aldehyde, gas phase purity 98.9%, yield 93.1%.
Embodiment 4: the trans preparation to sulfydryl cinnamic aldehyde
The four-hole boiling flask of the 1000mL equipped with stirring, thermometer and addition funnel adds 300 grams of water, 10.0 gram potassium bicarbonate, it is warming up to 30 DEG C, drips 76.0 grams (0.5 moles) mixed solution to sulfydryl benzaldehyde, 66 gram of 40% acetaldehyde solution and 200 grams of methanol, within about 3 hours, finish. Hereafter react 2 hours in 30 DEG C. Regulating pH value with dilute hydrochloric acid is 6, extraction into ethyl acetate three times (sharing 450 grams), merge organic facies, 200 grams of saturated sodium-chloride washings, layering, anhydrous sodium sulfate (30 grams) dries organic facies, weak yellow liquid 81.0 grams is obtained after precipitation, it is trans to sulfydryl cinnamic aldehyde, gas phase purity 99.1%, yield 91.0%.
Embodiment 5: the trans preparation to sulfydryl cinnamic aldehyde
The four-hole boiling flask of the 1000mL equipped with stirring, thermometer and addition funnel adds 300 grams of water, 2.0 grams of sodium hydroxide, it is warming up to 30 DEG C, drips 76.0 grams (0.5 moles) mixed solution to sulfydryl benzaldehyde, 66 gram of 40% acetaldehyde solution and 200 grams of methanol, within about 3 hours, finish. Hereafter react 2 hours in 30 DEG C. Regulating pH value with dilute hydrochloric acid is 6, extraction into ethyl acetate three times (sharing 450 grams), merge organic facies, 200 grams of saturated sodium-chloride washings, layering, anhydrous sodium sulfate (30 grams) dries organic facies, weak yellow liquid 70.3 grams is obtained after precipitation, it is trans to sulfydryl cinnamic aldehyde, gas phase purity 98.7%, yield 79.0%.
Three, the trans preparation to first sulfydryl cinnamyl alcohol (I)
Embodiment 6:
Equipped with stirring, the 500mL of thermometer four-hole boiling flask in add 44.5 grams trans to sulfydryl cinnamic aldehyde (0.25 mole), 200 grams of methanol, between keeping 15 degree to 25 DEG C, gradation 3.3 grams of sodium borohydrides of addition, finish, 25 DEG C of stirring reactions 2 hours. Recovered under reduced pressure methanol, adds 300 grams of water in residue, and regulating pH value with dilute hydrochloric acid is 7, extraction into ethyl acetate three times (sharing 300 grams), merge organic facies, 100 grams of saturated sodium-chloride washings, layering, anhydrous sodium sulfate (10 grams) dries organic facies, after precipitation, 50% recrystallizing methanol obtains trans to first sulfydryl cinnamyl alcohol (I) white powdery solids 43.2 grams, purity 99.6%(HPLC), yield 96.0%, fusing point 91��92 DEG C.
Embodiment 7:
Equipped with stirring, the 500mL of thermometer four-hole boiling flask in add 44.5 grams trans to sulfydryl cinnamic aldehyde (0.25 mole), 200 grams of methanol, between keeping 15-25 DEG C, gradation 3.8 grams of potassium borohydrides of addition, finish, 25 DEG C of stirring reactions 2 hours. Recovered under reduced pressure methanol, adds 300 grams of water in residue, and regulating pH value with dilute hydrochloric acid is 7, extraction into ethyl acetate three times (sharing 300 grams), merge organic facies, 100 grams of saturated sodium-chloride washings, layering, anhydrous sodium sulfate (10 grams) dries organic facies, after precipitation, 50% recrystallizing methanol obtains trans to first sulfydryl cinnamyl alcohol (I) white powdery solids 41.5 grams, purity 99.8%(HPLC), yield 92.1%, fusing point 91��92 DEG C.
Claims (6)
1. a trans industrialized preparing process to first sulfydryl cinnamyl alcohol, with thioanisole for initial feed, comprises the following steps that
(1) thioanisole and formylation reagent carry out formylation reaction in organic solvent I, prepare sulfydryl benzaldehyde;
Described formylation reagent is N,N-dimethylformamide and phosphorus oxychloride, any one combination of solid phosgene;
Described organic solvent I is N,N-dimethylformamide; Described organic solvent I and the mass ratio of thioanisole are (0.8-3.5): 1;
Phosphorus oxychloride or the mol ratio of solid phosgene in described thioanisole and formylation reagent are 1:1.0 ~ 1.8;
Described formylation reaction is undertaken by with the next stage: under subzero 10 DEG C of conditions, phosphorus oxychloride in formylation reagent or solid phosgene are added drop-wise to thioanisole, N, in dinethylformamide and organic solvent I, then, react 1-3 hour at 0 DEG C, it is warming up to 20 DEG C again to react 1-3 hour, then heats to 60-70 DEG C and react 1-3 hour;
(2) under base catalyst exists, sulfydryl benzaldehyde is carried out aldol reaction with acetaldehyde or Metaldehyde in organic solvent II, prepare trans to sulfydryl cinnamic aldehyde;
Described base catalyst is potassium hydroxide, potassium acetate or potassium bicarbonate;
Described organic solvent II is methanol;
(3) in the presence of a reducing agent, by trans to sulfydryl cinnamic aldehyde in organic solvent II, carry out reduction reaction, obtain trans to sulfydryl cinnamyl alcohol;
Described reducing agent is sodium borohydride, potassium borohydride or sodium cyanoborohydride;
Step (3) described organic solvent II is identical with organic solvent II in step (2).
2. the trans synthetic method to first sulfydryl cinnamyl alcohol as claimed in claim 1; it is characterized in that in step (1); described formylation reagent is N; dinethylformamide and phosphorus oxychloride mol ratio (1.0-5): the combination of 1; or DMF and solid phosgene mol ratio (3.0-9.0): the combination of 1.
3. the trans synthetic method to first sulfydryl cinnamyl alcohol as claimed in claim 1, it is characterised in that in step (2), described acetaldehyde is the acetaldehyde solution of mass ratio 40 ~ 50%.
4. the trans synthetic method to first sulfydryl cinnamyl alcohol as claimed in claim 1, it is characterised in that in step (2), the described mol ratio to first sulfydryl benzaldehyde Yu acetaldehyde is 1:1.0-2.0.
5. the trans synthetic method to first sulfydryl cinnamyl alcohol as claimed in claim 1, it is characterised in that in step (2), reaction temperature is 0 DEG C of reflux temperature to organic solvent II.
6. the trans synthetic method to first sulfydryl cinnamyl alcohol as claimed in claim 1, it is characterised in that in step (3), the described trans mol ratio to sulfydryl cinnamic aldehyde and reducing agent is 1:0.25-0.5, and reaction temperature is 0 DEG C of reflux temperature to organic solvent II.
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| WO2002004411A1 (en) * | 2000-07-07 | 2002-01-17 | The Administrators Of The Tulane Educational Fund | Methods for protection of stratified squamous epithelium against injury by noxious substances and novel agents for use therefor |
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| WO2002004411A1 (en) * | 2000-07-07 | 2002-01-17 | The Administrators Of The Tulane Educational Fund | Methods for protection of stratified squamous epithelium against injury by noxious substances and novel agents for use therefor |
| FR2824555A1 (en) * | 2001-05-11 | 2002-11-15 | Poudres & Explosifs Ste Nale | Synthesis of a para-alkoxybenzaldehyde by formylation of a phenylethyl ether using a complex of a Vilsmeier salt with aluminium trichloride, useful in the preparation of medicaments and perfumes |
| CN1434031A (en) * | 2003-02-14 | 2003-08-06 | 武汉大学 | 2,5-dimethoxy-4-ethyl sulfide-beta-nitrostyrolene and preparation process and use thereof |
| CN1456550A (en) * | 2003-05-28 | 2003-11-19 | 武汉大学 | 2,5-dimethoxy-4-[2'-fluorosulphuric radical]-beta-nitro-styrene and its preparation and uses |
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