CN107245250A - A kind of method for synthesizing disperse red CNB - Google Patents
A kind of method for synthesizing disperse red CNB Download PDFInfo
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- CN107245250A CN107245250A CN201611260710.3A CN201611260710A CN107245250A CN 107245250 A CN107245250 A CN 107245250A CN 201611260710 A CN201611260710 A CN 201611260710A CN 107245250 A CN107245250 A CN 107245250A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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Abstract
The invention discloses a kind of method for synthesizing disperse red CNB, its step is：（1）Using chloroform as reaction dissolvent, using TBAB as phase transfer catalyst, using to a of propoxybenzaldehyde I as reaction raw materials, addition in the basic conditions, through hydrolyzed under acidic conditions obtain intermediate I b of p-propoxy mandelic acid the step of；（2）Using nitrobenzene as reaction dissolvent and oxidant, using the concentrated sulfuric acid as catalyst, with the c and b of p-propoxy mandelic acid I of 5 hydroxyl of condensation product, 2 oxo, 32,3 Dihydrobenzofuranes of phenyl I for reaction raw materials, the step of obtaining target product through cyclization oxidation reaction.The present invention is using nitrobenzene as reaction dissolvent and oxidant, and cyclization and oxidation Liang Ge workshop sections are almost carried out simultaneously, and the later stage of the workshop section is by lifting temperature, ensure that oxidation reaction is carried out thorough, therefore, the ratio that whole cyclization oxidation section all reacts more thoroughly, so as to obtain higher yield.
Description
Technical field
The present invention relates to a kind of synthetic method of disperse red, specific is exactly disperse red CNB synthetic method, belongs to chemical industry
The manufacturing technology field of dyestuff.
Background technology
Disperse red CNB is also known as disperse red 356, CAS:159968-00-0, chemical entitled (the 4- propoxyl group benzene of 3- phenyl -7
Base) two furans -2,6- diketone of-benzo is the maximum kind of ketocoumaran disperse dyes, disperse red CNB is with its color and luster
Bright-coloured coloring intensity is high and dyeability is good, is particularly the excellent properties shown in polyester superfine fibre application and obtains
Pay attention to extensively.Disperse red CNB structural formulas are：
Domestic existing disperse red CNB production method, which is mainly, is synthesized by the following way route completion：
It is related to violent in toxicity Cymag in above-mentioned synthetic reaction, and also has hypertoxic gas hydrogen cyanide in cyanogenation workshop section
Produce, belong to high-risk reaction, therefore the workshop section is particularly severe to safety and environmental protection measure.Other said synthesis route yield is low, only
50% or so, production cost is also higher.Although making many improvement, such as condensation product around said synthesis route both at home and abroad
Process optimization, the selection of oxidant, the addition of catalyst, the selection of reaction dissolvent etc., although yield has obtained certain carry
Height, but effect is not notable, production cost is still high, and product quality falls flat.To find out its cause, main
Come from two aspects, first, the excess of condensation product causes the tar produced in cyclization oxidizing process excessive, so as to cause product
Quality Down, the excessive solid waste of generation；Second, the selection of oxidant, such as tetrachloro cyanogen quinone, tetrachloroquinone price are higher, cause into
This is high.
The content of the invention
The present invention is in order to overcome the hypertoxic gas hydrogen cyanide of generation in above-mentioned technique, product yield is low, quality is unstable, product
Cost is high, it is proposed that a kind of new synthesis disperse red CNB method.
Technical scheme is summarized as follows：A kind of method for synthesizing disperse red CNB, is mainly included the following steps that：
(1) addition-hydrolysis
Synthetic route：
Using chloroform as reaction dissolvent, using TBAB as phase transfer catalyst, using to propoxybenzaldehyde as reaction raw materials,
Addition in the basic conditions, a wherein intermediate p-propoxy mandelic acid is obtained through hydrolyzed under acidic conditions.
Operating procedure：By a certain amount of chloroform and to propoxybenzaldehyde input reactor stirring, add on a small quantity
TBAB, and temperature control is started to be added dropwise certain density liquid caustic soda in a certain scope, time for adding is controlled in more than 8h, dripped
Bi Baowen a few hours, TLC tracking, to disappear the raw material point of propoxybenzaldehyde for reaction end, reaction, which is finished, is down to normal temperature,
Quantitative water and chloroform is added, stirring a moment, layering removes organic layer, a small amount of chloroform is added into water layer stirring sheet
Carve, then be layered, remove organic layer, gained organic layer merges, distills, reclaims chloroform twice.Then start to carry out water layer
Hydrochloric acid (30w%) is added dropwise, and is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50 DEG C of vacuum
24h is dried, it is stand-by.
(2) cyclization-oxidation reaction
Synthetic route：
Using nitrobenzene as reaction dissolvent and oxidant, using sulfuric acid as catalyst, with condensation product 5- hydroxyl -2- oxo -3- benzene
Base -2,3- Dihydrobenzofuranes and p-propoxy mandelic acid are reaction raw materials.
Operating procedure：A certain amount of nitrobenzene and a small amount of sulfuric acid are put into reactor, add quantitative condensation product and
P-propoxy mandelic acid, is warming up to certain temperature and starts to be incubated a few hours, controlled in HPLC, with the content of p-propoxy mandelic acid
Be reaction end no more than 2%, reaction finishes, by temperature on the basis of original on be adjusted to certain temperature, start to be incubated number
Hour, HPLC continues to track, and no more than 2% is reaction end with cyclocomplex, reaction is finished, and is cooled near 70 DEG C, is not closed
Heating system, starts that a certain amount of methanol, 1/2nd quantity of methyl alcohol requirement completion of dropping, the first of remaining half in 3h is added dropwise
Alcohol completion of dropping in 1h, slow cooling is to 40~45 DEG C, and suction filtration, filter cake soaks 0.5h with methanol, and after draining, hot wash is extremely
Colourless, drying obtains kermesinus dyestuff i.e. target product.
The present invention has following remarkable advantage compared with prior art：(1) avoid using violent in toxicity Cymag, eliminate height
The risk of danger operation, also alleviates the pressure that environmental protection treatment cyanide wastewater is brought significantly；(2) nitrobenzene is not only reaction dissolvent,
It is also oxidant, therefore compared with the reaction dissolvents such as traditional toluene, o-dichlorohenzene, acetic acid, with significant superiority, i.e. ring
Oxidant need not be added by closing the oxidation section after terminating.Operating procedure is not only reduced, and reduces synthesis cost；(3)
Nitrobenzene is preferable to the solubility property of condensation product compared with toluene, o-dichlorohenzene, acetic acid etc., and products therefrom residual tar is less,
Therefore product quality is preferable；(4) reduction condensation product consumption make its mole slightly excessive, therefore condensation product high temperature polymerization and point
The possibility reduction of solution, so as to reduce the amount of tar in reaction system；(5) nitrobenzene is used as reaction dissolvent and oxidant, ring
Close and oxidation Liang Ge workshop sections are almost carried out simultaneously, the later stage of the workshop section is by lifting temperature, it is ensured that oxidation reaction progress is thorough, because
This, the ratio that whole cyclization oxidation section all reacts more thoroughly, so as to obtain higher yield.
Embodiment
Specific reactions steps are as follows：
(1) addition-hydrolysis：Reactor stirring sheet is put into by a certain amount of chloroform and to propoxybenzaldehyde
Carve, add a small amount of TBAB, wherein chloroform and the mass ratio to propoxybenzaldehyde are 5:1, TBAB with to propoxyl group benzene
The mass ratio of formaldehyde is 0.2~1:10, and the scope by temperature control at 25~65 DEG C, then starting dropwise addition mass fraction is
30%~50% liquid caustic soda, liquid caustic soda is 4~6 with the mass ratio to propoxybenzaldehyde:1, time for adding control is in more than 8h, drop
Bi Baowen a few hours are added, TLC tracking, to disappear the raw material point of propoxybenzaldehyde for reaction end, is reacted to finish and is down to
Normal temperature, adds quantitative water and chloroform, and water is 2.5 with the mass ratio to propoxybenzaldehyde:1, three chloromethanes that need to be added
Alkane is 2.5 with the mass ratio to propoxybenzaldehyde:1, in stirring a moment, stand, be layered, remove lower organic layer, leave water layer,
Then a small amount of chloroform is added into water layer again, now chloroform and the mass ratio to propoxybenzaldehyde are 1.5:1, stir
A moment is mixed, stands, be layered, organic layer is removed.Gained organic layer merges, distills, reclaims chloroform twice.Then start to water
Layer carries out hydrochloric acid dropwise addition, and time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid to the third oxygen
Base mandelic acid, 50 DEG C are dried in vacuo 24h, stand-by.
(2) cyclization-oxidation reaction：A certain amount of nitrobenzene and a small amount of sulfuric acid are put into reactor, added quantitative
The mass ratio of condensation product and p-propoxy mandelic acid, wherein nitrobenzene and p-propoxy mandelic acid is 5:1, sulfuric acid and nitrobenzene
Mass ratio is 0.5~1:40, the mass ratio of condensation product and p-propoxy mandelic acid is 1.3~1.6:1.90~95 DEG C are warming up to open
Begin insulation a few hours, control in HPLC, no more than 2% be reaction end with the content of p-propoxy mandelic acid, reaction is finished, by temperature
Degree raises 5~10 DEG C on the basis of original, starts to be incubated a few hours, and HPLC continues to track, and no more than 2% is anti-with cyclocomplex
Terminal is answered, reaction is finished, be cooled near 70 DEG C, do not close heating system, start that a certain amount of methanol, methanol and nitro is added dropwise
The mass ratio of benzene is 1.5~2.5:1,1/2nd quantity of methyl alcohol requirement completion of dropping in 3h, the methanol of remaining half is in 1h
Interior completion of dropping, slow cooling is to 40~45 DEG C, suction filtration, and filter cake soaks 0.5h with methanol, after draining, hot wash to colourless,
Drying, obtains kermesinus dyestuff.
Embodiment 1
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 0.8g TBAB, continue to stir, 30w% liquid caustic soda 240g, reaction temperature is at the uniform velocity added dropwise in 25 DEG C of beginnings
Degree is no more than 30 DEG C, and 10h completion of dropping starts insulation, and TLC tracking is incubated 5h, raw material point disappears, anti-to propoxybenzaldehyde
Should be complete, stop being incubated, 100g water and 100g chloroform are added at such a temperature, in stirring a moment, stands, be layered, remove
Sub-cloud organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, is layered, by lower floor
Organic layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out hydrochloric acid (30w%) to water layer
It is added dropwise, time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50
DEG C vacuum drying 24h, obtain dry product 46.2g, yield 92.4% is stand-by.
(2) preparation of target product：231g nitrobenzene and 2.9g sulfuric acid are put into reactor, stirred, is added
60g condensation product and 46.2g p-propoxy mandelic acid, are warming up to 90 DEG C, are controlled in HPLC, are incubated 5h, raw material remnants 1.7%,
Start upper temperature regulating to 95 DEG C, HPLC continues to track, and is incubated 7h, cyclocomplex remnants 1.2%, starts to be cooled to 70 DEG C, first is added dropwise
Alcohol 345g, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h, after draining, hot wash with methanol
To colourless, drying, kermesinus dyestuff is obtained.Dry, weigh, obtain dry product 70.2g, yield 78.56%.Testing result such as Tables 1 and 2
It is shown.
Embodiment 2
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 30w% liquid caustic soda 240g, reaction temperature is at the uniform velocity added dropwise in 25 DEG C of beginnings
No more than 30 DEG C, 10h completion of dropping starts insulation, and TLC tracking is incubated 3.5h, raw material point disappears, anti-to propoxybenzaldehyde
Should be complete, stop being incubated, 100g water and 100g chloroform are added at such a temperature, in stirring a moment, stands, be layered, remove
Sub-cloud organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, is layered, by lower floor
Organic layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out hydrochloric acid (30w%) to water layer
It is added dropwise, time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50
DEG C vacuum drying 24h, obtain dry product 45.4g, yield 90.8% is stand-by.
(2) preparation of target product：227g nitrobenzene and 5.7g sulfuric acid are put into reactor, stirred, is added
59g condensation product and 46.2g p-propoxy mandelic acid, are warming up to 90 DEG C, are controlled in HPLC, are incubated 4h, raw material remnants 1.5%,
Start upper temperature regulating to 95 DEG C, HPLC continues to track, and is incubated 7h, cyclocomplex remnants 1.6%, starts to be cooled to 70 DEG C, first is added dropwise
Alcohol 340g, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h, after draining, hot wash with methanol
To colourless, drying, kermesinus dyestuff is obtained.Dry, weigh, obtain dry product 68.4g, yield 76.54%.Testing result such as Tables 1 and 2
It is shown.
Embodiment 3
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 30w% liquid caustic soda 240g, reaction temperature is at the uniform velocity added dropwise in 50 DEG C of beginnings
No more than 65 DEG C, 10h completion of dropping starts insulation, and TLC tracking is incubated 1.5h, raw material point disappears, anti-to propoxybenzaldehyde
Should be complete, stop being incubated, 100g water and 100g chloroform are added at such a temperature, in stirring a moment, stands, be layered, remove
Sub-cloud organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, is layered, by lower floor
Organic layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out hydrochloric acid (30w%) to water layer
It is added dropwise, time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50
DEG C vacuum drying 24h, obtain dry product 45.8g, yield 91.6% is stand-by.
(2) preparation of target product：229g nitrobenzene and 2.9g sulfuric acid are put into reactor, stirred, is added
59.5g condensation product and 45.8g p-propoxy mandelic acid, are warming up to 95 DEG C, are controlled in HPLC, are incubated 4h, and raw material is remaining
1.8%, start upper temperature regulating to 100 DEG C, HPLC continues to track, and is incubated 5h, cyclocomplex remnants 1.5%, starts to be cooled to 70 DEG C,
Methanol 343g is added dropwise, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h with methanol, after draining, heat
Water washing obtains kermesinus dyestuff to colourless, drying.Dry, weigh, obtain dry product 67.5g, yield 75.54%.Testing result such as table
1 and table 2 shown in.
Embodiment 4
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 30w% liquid caustic soda 240g is at the uniform velocity added dropwise in 65 DEG C of beginnings, is opened during dropwise addition
Begin to flow back, temperature no longer rises, 10h completion of dropping, start insulation, TLC tracking is incubated 0.5h, raw material point disappears, to propoxyl group
Benzaldehyde reaction is complete, stops insulation, at such a temperature addition 100g water and 100g chloroform, stirring a moment, stand,
Layering, removes lower organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, divides
Layer, lower organic layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out salt to water layer
Sour (30w%) is added dropwise, and time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid to propoxyl group
Mandelic acid, 50 DEG C of vacuum drying 24h, obtains dry product 46.1g, yield 92.2% is stand-by.
(2) preparation of target product：230.5g nitrobenzene and 2.9g sulfuric acid are put into reactor, stirred, plus
Enter 60g condensation product and 46.1g p-propoxy mandelic acid, be warming up to 95 DEG C, controlled in HPLC, be incubated 4h, raw material is remaining
1.4%, start upper temperature regulating to 105 DEG C, HPLC continues to track, and is incubated 4h, cyclocomplex remnants 1.7%, starts to be cooled to 70 DEG C,
Methanol 346g is added dropwise, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h with methanol, after draining, heat
Water washing obtains kermesinus dyestuff to colourless, drying.Dry, weigh, obtain dry product 66.8g, yield 74.75%.Testing result such as table
1 and table 2 shown in.
Embodiment 5
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 50w% liquid caustic soda 160g is at the uniform velocity added dropwise in 25 DEG C of beginnings, temperature does not surpass
30 DEG C are crossed, 8h completion of dropping starts insulation, and TLC tracking is incubated 3h, and raw material point disappears, and reacts complete to propoxybenzaldehyde,
Stop being incubated, 100g water and 100g chloroform are added at such a temperature, in stirring a moment, stands, be layered, except sub-cloud has
Machine layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, is layered, by lower organic layer point
Go out and merge with the organic layer separated for the first time, reclaim chloroform.Then start to carry out water layer hydrochloric acid (30w%) dropwise addition, drop
It is not less than 1h between added-time, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50 DEG C of vacuum
24h is dried, dry product 45.4g is obtained, yield 90.8% is stand-by.
(2) preparation of target product：227g nitrobenzene and 2.8g sulfuric acid are put into reactor, stirred, is added
72.6g condensation product and 45.4g p-propoxy mandelic acid, are warming up to 95 DEG C, are controlled in HPLC, are incubated 4h, and raw material is remaining
1.2%, start upper temperature regulating to 105 DEG C, HPLC continues to track, and is incubated 4h, cyclocomplex remnants 1.5%, starts to be cooled to 70 DEG C,
Methanol 340g is added dropwise, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h with methanol, after draining, heat
Water washing obtains kermesinus dyestuff to colourless, drying.Dry, weigh, obtain dry product 68.3g, yield 76.43%.Testing result such as table
1 and table 2 shown in.
Embodiment 6
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 50w% liquid caustic soda 160g is at the uniform velocity added dropwise in 50 DEG C of beginnings, temperature does not surpass
65 DEG C are crossed, 8h completion of dropping starts insulation, and TLC tracking is incubated 1.5h, and raw material point disappears, propoxybenzaldehyde has been reacted
Entirely, stop being incubated, 100g water and 100g chloroform are added at such a temperature, in stirring a moment, stands, be layered, under removing
Layer organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, is layered, lower floor is organic
Layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out water layer hydrochloric acid (30w%) drop
Plus, time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50 DEG C
24h is dried in vacuo, dry product 46.8g is obtained, yield 93.6% is stand-by.
(2) preparation of target product：234g nitrobenzene and 2.9g sulfuric acid are put into reactor, stirred, is added
74.9g condensation product and 46.8g p-propoxy mandelic acid, are warming up to 95 DEG C, are controlled in HPLC, are incubated 4h, and raw material is remaining
1.7%, start upper temperature regulating to 105 DEG C, HPLC continues to track, and is incubated 4h, cyclocomplex remnants 1.4%, starts to be cooled to 70 DEG C,
Methanol 351g is added dropwise, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h with methanol, after draining, heat
Water washing obtains kermesinus dyestuff to colourless, drying.Dry, weigh, obtain dry product 68.6g, yield 76.77%.Testing result such as table
1 and table 2 shown in.
Embodiment 7
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 50w% liquid caustic soda 160g is at the uniform velocity added dropwise in 65 DEG C of beginnings, is opened during dropwise addition
Begin to flow back, temperature no longer rises, 8h completion of dropping, start insulation, TLC tracking is incubated 0.5h, raw material point disappears, to propoxyl group
Benzaldehyde reaction is complete, stops insulation, at such a temperature addition 100g water and 100g chloroform, stirring a moment, stand,
Layering, removes lower organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, divides
Layer, lower organic layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out salt to water layer
Sour (30w%) is added dropwise, and time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid to propoxyl group
Mandelic acid, 50 DEG C of vacuum drying 24h, obtains dry product 45.7g, yield 91.4% is stand-by.
(2) preparation of target product：228.5g nitrobenzene and 2.9g sulfuric acid are put into reactor, stirred, plus
Enter 73.1g condensation product and 45.7g p-propoxy mandelic acid, be warming up to 95 DEG C, controlled in HPLC, be incubated 4h, raw material is remaining
1.4%, start upper temperature regulating to 105 DEG C, HPLC continues to track, and is incubated 4h, cyclocomplex remnants 1.7%, starts to be cooled to 70 DEG C,
Methanol 343g is added dropwise, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h with methanol, after draining, heat
Water washing obtains kermesinus dyestuff to colourless, drying.Dry, weigh, obtain dry product 67.9g, yield 75.98%.Testing result such as table
1 and table 2 shown in.
Embodiment 8
(1) preparation calculated propoxyl group almond：200g chloroform and being put into propoxybenzaldehyde for 40g are reacted
In device, stir, add 4g TBAB, continue to stir, 50w% liquid caustic soda 160g is at the uniform velocity added dropwise in 50 DEG C of beginnings, temperature does not surpass
65 DEG C are crossed, 8h completion of dropping starts insulation, and TLC tracking is incubated 1.5h, and raw material point disappears, propoxybenzaldehyde has been reacted
Entirely, stop being incubated, 100g water and 100g chloroform are added at such a temperature, in stirring a moment, stands, be layered, under removing
Layer organic layer, leaves water layer.Then 60g chloroform is added into water layer again, in stirring a moment, stands, is layered, lower floor is organic
Layer is separated and merged with the organic layer separated for the first time, reclaims chloroform.Then start to carry out water layer hydrochloric acid (30w%) drop
Plus, time for adding is not less than 1h, is terminal with pH ＜ 3.1h is stirred, filtering obtains faint yellow solid p-propoxy mandelic acid, 50 DEG C
24h is dried in vacuo, dry product 46.4g is obtained, yield 92.8% is stand-by.
(2) preparation of target product：232g nitrobenzene and 2.9g sulfuric acid are put into reactor, stirred, is added
74.2g condensation product and 46.4g p-propoxy mandelic acid, are warming up to 95 DEG C, are controlled in HPLC, are incubated 4h, and raw material is remaining
1.6%, start upper temperature regulating to 105 DEG C, HPLC continues to track, and is incubated 4h, cyclocomplex remnants 1.4%, starts to be cooled to 70 DEG C,
Methanol 580g is added dropwise, time for adding is controlled in 4h, is down to less than 45 DEG C, suction filtration, filter cake soaks 0.5h with methanol, after draining, heat
Water washing obtains kermesinus dyestuff to colourless, drying.Dry, weigh, obtain dry product 70.03g, yield 78.36%.Testing result is such as
Shown in Tables 1 and 2.
According to above-described embodiment, it is known that preferred processing condition is：
(1) in the preparation calculated propoxyl group almond, reaction reagent chloroform is with the mass ratio to propoxybenzaldehyde
5:1, the chloroform and water once added are 2.5 with the mass ratio to propoxybenzaldehyde:1, secondary three chloromethanes added
Alkane is 1.5 with the mass ratio to propoxybenzaldehyde:1.TBAB is 0.2~1 with the mass ratio to propoxybenzaldehyde:10.Liquid
Alkali mass fraction is 30%~50%, and liquid caustic soda is 4~6 with the mass ratio to propoxybenzaldehyde:1, reaction temperature is 25~65
DEG C, liquid caustic soda time for adding is in more than 8h.The amount that hydrochloric acid is added dropwise during acidifying is defined by pH ＜ 3.The dried strip of p-propoxy mandelic acid
Part is 50 DEG C of vacuum drying 24h.
(2) mass ratio of the described nitrobenzene of target product preparation and p-propoxy mandelic acid is 5:1, sulfuric acid and nitrobenzene
Mass ratio be 0.5~1:40, the mass ratio of condensation product and p-propoxy mandelic acid is 1.3~1.6:1, methanol and nitrobenzene
Mass ratio is 1.5~2.5:1.Cyclization temperature is 90~95 DEG C, and oxidizing temperature is 95~105 DEG C.Parameter is controlled in HPLC：Raw material point
P-propoxy mandelic acid and cyclocomplex are no more than 2%.
The single sample coloured light testing experiment result of table 1 is counted
The single sample color fastness testing experiment result of table 2 is counted
。
Claims (5)
1. disperse red CNB of the synthesis with structure shown in formula I method,
Characterized in that, the described method comprises the following steps：
(1) using chloroform as reaction dissolvent, using TBAB as phase transfer catalyst, using former as reaction to a of propoxybenzaldehyde I
Material, in the basic conditions addition, the step of obtaining intermediate I b of p-propoxy mandelic acid through hydrolyzed under acidic conditions；
(2) using nitrobenzene as reaction dissolvent and oxidant, using the concentrated sulfuric acid as catalyst, with condensation product 5- hydroxyl -2- oxo -3- benzene
The c of base -2, the 3- Dihydrobenzofuranes I and b of p-propoxy mandelic acid I is reaction raw materials, and target product is obtained through cyclization-oxidation reaction
The step of；
2. the method as described in claim 1, it is characterised in that wherein in step (1), TBAB and the matter to propoxybenzaldehyde
Amount is than being 0.2~1:10.
3. the method as described in claim 1, it is characterised in that wherein in step (1), reaction temperature is 25~65 DEG C.
4. the method as described in claim 1, it is characterised in that wherein in step (2), nitrobenzene and p-propoxy mandelic acid
Mass ratio is 5:1, the mass ratio of the concentrated sulfuric acid and nitrobenzene is 0.5~1:40,5- hydroxyl -2- oxo -3- phenyl -2,3- dihydrobenzenes
And the mass ratio of furans and p-propoxy mandelic acid is 1.3~1.6:1.
5. the method as described in claim 1, it is characterised in that wherein in step (2), cyclization temperature is 90~95 DEG C, oxidation
Temperature is 95~105 DEG C.
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Citations (4)
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| CN1786080A (en) * | 2005-01-14 | 2006-06-14 | 阮加根 | Preparation process of benzodifuranone disperse red dye and product thereof |
| CN1852883A (en) * | 2003-09-19 | 2006-10-25 | 京仁洋行 | Alpha-hydroxy-benzeneacetic acid derivatives, and compounds having two 5-membered lactone rings fused to central cyclohexa-1,4-diene nucleus based upon the same, and uses of the compounds |
| CN1955154A (en) * | 2006-07-06 | 2007-05-02 | 姚献东 | Preparation method of alkoxyl mandelic acid |
| CN101717403A (en) * | 2009-11-13 | 2010-06-02 | 浙江工业大学 | New green synthesizing process for ketocoumaran compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1852883A (en) * | 2003-09-19 | 2006-10-25 | 京仁洋行 | Alpha-hydroxy-benzeneacetic acid derivatives, and compounds having two 5-membered lactone rings fused to central cyclohexa-1,4-diene nucleus based upon the same, and uses of the compounds |
| CN1786080A (en) * | 2005-01-14 | 2006-06-14 | 阮加根 | Preparation process of benzodifuranone disperse red dye and product thereof |
| CN1955154A (en) * | 2006-07-06 | 2007-05-02 | 姚献东 | Preparation method of alkoxyl mandelic acid |
| CN101717403A (en) * | 2009-11-13 | 2010-06-02 | 浙江工业大学 | New green synthesizing process for ketocoumaran compound |
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