CN109879770A

CN109879770A - A kind of compound and preparation method thereof, purposes

Info

Publication number: CN109879770A
Application number: CN201910326452.1A
Authority: CN
Inventors: 童国林; 史蕊; 李寿椿
Original assignee: Nanjing Forestry University
Current assignee: Nanjing Forestry University
Priority date: 2019-04-23
Filing date: 2019-04-23
Publication date: 2019-06-14
Anticipated expiration: 2039-04-23
Also published as: CN109879770B

Abstract

The present invention provides a kind of compounds and preparation method thereof, purposes.A kind of compound has the structure of logical formula (I):Wherein, R₁、R₂、R₃、R₄And R₅In at least one be amino, remaining is independently selected from H, halogen, the substituted or unsubstituted C of hetero atom_1‑20Alkyl.Active group-the COF of the compound is easy to react with the active group (hydroxyl, amino etc.) of cellulose surface, and not facile hydrolysis in itself, therefore manufactured azo dyes has very strong stability in water, and colouring power is strong.

Description

A kind of compound and preparation method thereof, purposes

Technical field

The present invention relates to organic synthesis fields, more particularly, to a kind of compound and preparation method thereof, purposes.

Background technique

Introducing Cyanuric Chloride isoreactivity group in aromatic compound intramolecular is that dye industry prepares dyestuff intermediate One of important method.The dyestuff synthesized with these dyestuff intermediates, since the active group in molecular structure can be with hydroxyl on fiber Base or amino react to form the covalent bonds such as C-O or C-N, so that dye molecule firm connection is on the fabric.It can answer extensively For weaving, the dyeing in the fields such as papermaking and leather.

But using the reactive dye that this dyestuff intermediate of Cyanuric Chloride synthesizes often exist low degree of fixation, facile hydrolysis and The problems such as wastewater treatment is difficult.The type and performance of midbody compound drastically influence the performance of the subsequent product of synthesis and refer to Mark.Therefore extension has the intermediate type of excellent activity, and tool has very important significance.

In view of this, the present invention is specifically proposed.

Summary of the invention

The first object of the present invention is to provide a kind of compound, the active group-COF of the compound, be easy with it is fine The active group (hydroxyl, amino etc.) for tieing up plain surface reacts, and not facile hydrolysis itself, therefore manufactured azo dyes exists There is very strong stability, and colouring power is strong in water.

The second object of the present invention is to provide the purposes of above compound, is mainly used for dye field, compound warp Cross after diazotising from can obtain different types of dyestuff after different coupling agents.

The third object of the present invention is to provide the preparation method of above compound, and this method synthetic route is simple, reaction Simply, by-product is few.

In order to solve the above technical problems, the present invention provides following technical schemes:

A kind of compound has the structure of logical formula (I):

Wherein, R₁、R₂、R₃、R₄And R₅In at least one be amino, remaining independently selected from H, halogen, hetero atom replace Or unsubstituted C_1-20Alkyl；

Preferably, the hetero atom replaces C_1-20Alkyl is C_1-20Alkoxy or C_1-20Alkylthio group.

- COF and amino can be with ortho positions, meta or para position in the compound.

There is diazotizing amino, it is often more important that containing can be with the active group-of fiber-reactive in compound (I) COF ,-COF have the advantage that as the active group in conjunction with cellulose

1, binding ability is strong, i.e. F is easy to leave away, and following reaction (formula (one)) occurs,

Cell-OH indicates cellulose；

2, the nonmetal character of F is strong, and the stability after leaving away in conjunction with hydrogen is strong (i.e. the stability of hydrogen fluoride is strong), so that containing There is the compound of this active group to be easier to be combined with each other with fiber, reacts and carried out to forward direction, while is above-mentioned compared with hydrolysis Reaction equation (one) is competitive stronger；

3 ,-the COF in the compound is as the bridging between dyestuff and fiber, since molecular weight lower (47) leads to activity The accounting of facile hydrolysis component is lower in dyestuff, this can not only reduce dye dosage, but also can increase the reactivity worth of dyestuff；

4, the compound is a kind of intermediate with excellent activity, and can be used for preparing has not facile hydrolysis and be easy to and fibre Reactive dye, pharmaceuticals of the binding characteristics such as dimension, protein etc..

In the present invention, R₁、R₂、R₃、R₄And R₅Selected halogen can be fluorine, chlorine, bromine or iodine；C_1-20Alkyl can be C_1-20 Alkyl, C_1-20Alkylene or C_1-20The C that aryl or hetero atom replace_1-20Alkyl, C_1-20Alkylene or C_1-20Aryl；C_1-20 Alkyl can be direct-connected or branch or cyclic hydrocarbon radical.

C_1-20Alkyl such as methyl, ethyl, methylmethylene, propyl, isopropyl, butyl or its isomers, amyl or its is different Structure body, hexyl or its isomers, nonyl or its isomers, decyl or its isomers, eicosyl or its isomers, vinyl or Its isomers, acrylic or its isomers, cyclobutenyl or its isomers, pentenyl or its isomers, hexenyl or its isomers, Icosa alkene alkyl or its isomers, benzyl or its isomers, phenylpropyl or its isomers, benzene butyl or its isomers, naphthalene first Base or its isomers, or the above alkyl hetero atom replace, hetero atom includes N, S, O, P etc..

Each substituent group in mutual-through type of the present invention advanced optimizes as follows.

Preferably, in some embodiments of the present invention, R₁、R₂、R₃、R₄And R₅In at least one be amino, remaining independence Ground is selected from H, halogen, C_1-10The C that alkyl or hetero atom replace_1-10Alkyl.

Preferably, in some embodiments of the present invention,

R₁For amino；

R₂For hydrogen, halogen, C_1-5The C that alkyl or hetero atom replace_1-5Alkyl；

R₃For hydrogen, halogen, C_1-5The C that alkyl or hetero atom replace_1-5Alkyl；

R₄For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-3Alkyl；

R₅For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-3Alkyl.

Preferably, in some embodiments of the present invention,

R₁For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-3Alkyl；

R₂For amino；

R₃For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-3Alkyl；

R₄For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-5Alkyl；

R₅For hydrogen, halogen, C_1-5The C that alkyl or hetero atom replace_1-5Alkyl.

Preferably, in some embodiments of the present invention,

R₁For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-5Alkyl；

R₂For hydrogen, halogen, C_1-3The C that alkyl or hetero atom replace_1-3Alkyl；

R₃For amino；

Preferably, in some embodiments of the present invention, the compound of the logical formula (I) is one of following:

Compound (I) provided by the invention mainly synthesizes by three-step reaction, and route is as follows:

Include the following steps:

A, make the compound of logical formula (II) that chlorination reaction occur, obtain the compound of logical formula (III)；

Wherein, R₁’、R₂’、R₃’、R₄' and R₅' at least one be amide groups or alkoxycarbonyl amido, remaining is independently The alkyl replaced selected from H, halogen, alkyl or hetero atom；

B, it reacts the compound of logical formula (III) with fluorization agent, obtains the compound of logical formula (IV)；

C, the compound of logical formula (IV) is made to slough the acyl group of the amide groups or the alkoxy carbonyl group of the alkoxycarbonyl amido, Obtain the compound of logical formula (I).

Wherein, lead to the R of formula (II)₁’、R₂’、R₃’、R₄' and R₅' correspond respectively to the R led in formula (I)₁、R₂、R₃、R₄And R₅, Difference is only the raw material selected when synthesizing by acyl group or alkoxycarbonyl amido of the amino replacement for amide groups in the latter Amino is protected.

Step a is to generate acyl chlorides, and chlorinating agent used can be in phosphorus trichloride, phosphorus pentachloride and thionyl chloride It is one or more；

The step b is to be replaced chlorine in acyl chlorides with fluorization agent, and inorganic fluorinating agent or organic fluoriding agents can be used, such as NH₄F、LiF、NaF、KF、CsF、AgF、SbF₃、BrF₃、MnF₃、CuF、(CH₃)₄NF and its hydrochlorate or (C₄H₉)₄NF and its ackd salt One of or it is a variety of.

If slough the acyl group of the amide groups in the step c, hydrolyze the compound of logical formula (IV) in acid, water Preferred 20-200 DEG C of temperature of solution, the preferred 1-48h of hydrolysis time.

If slough the alkoxy carbonyl group of the alkoxycarbonyl amido in the step c, make the compound for catalysis of logical formula (IV) Hydrogenolysis, acid cleavage or reduction (Na/NH₃(liquid) makees reducing agent).Wherein, H is used when catalytic hydrogenolysis₂Or other hydrogen donors, general room temperature Hydrogenated at normal pressure.When there is group sensitive to catalytic hydrogenolysis or catalyst deactivation in molecule, acid cleavage or reduction side Method is more applicable.Meanwhile to avoid generating by-product, the acid for acidolysis cracking is preferably HBr etc..

The above three-step reaction is in addition to compound (II), and without other complicated organic matter, and reaction condition is simple, secondary Product is high, and compound (I) combined coefficient and yield is greatly improved in this.

To sum up, compared with prior art, invention achieves following technical effects:

(1) this kind of compound that the present invention synthesizes can be used as organic synthesis intermediate, be primarily useful for dye industry, synthesize Obtained organic matter is easy in conjunction with the compounds containing-OH such as fiber since the presence of acyl fluorides group will have without facile hydrolysis Characteristic；

(2) synthetic method by-product of the invention is few, and target product yield is high.

Detailed description of the invention

It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.

Fig. 1 is the nuclear-magnetism F spectrogram for the compound I that the embodiment of the present invention 1 synthesizes；

Fig. 2 is the IR Characterization map for the compound I that the embodiment of the present invention 1 synthesizes.

Specific embodiment

Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.

Embodiment 1

Synthesize compound I

Synthetic route is as follows:

1)

2)

3)

1) the compound A1 of 181kg is added in a kettle, according to SOCl₂Molar ratio with compound A1 will for 1:1 SOCl₂It is added in reaction kettle, is warming up to 125 ± 5 DEG C, chlorine acylation is carried out under stirring condition, reaction time 12h is produced Raw HCl and SO₂Gas is pumped into collecting tank using vacuum, obtains compound B-11 after reaction；

2) dry compound B-11 is added in reaction vessel, is warming up to 75 ± 5 DEG C, predissolve and the NaF in water is added Enter in the reaction vessel, in 75 ± 5 DEG C of reaction 4-5h, after reaction dries product Compound C1；Wherein, compound B-11 with The molar ratio of NaF is 1:2.5；

3) compound C1 obtained in step 2) is added in reaction vessel, is added into the reaction vessel a certain amount of HCl solution dissolves compound C1, is stirred to react, speed of agitator 1500rpm, and reaction temperature is 80-135 DEG C, the present embodiment Specially 90-100 DEG C, reaction extracts reaction solution and supernatant is collected by centrifugation when deposit-free, will collect obtained supernatant and use Alkalimetric titration, such as titration generate a large amount of target products, then stop reacting.

Compound I 134.8kg is prepared through the above steps, the yield of compound I is 97%.

The nuclear-magnetism F spectrum and infared spectrum difference of compound I is as illustrated in fig. 1 and 2.

Following each structures of embodiment have carried out structural characterization also by nuclear-magnetism F spectrum and infared spectrum, do not repeat below.

Embodiment 2

Synthesize compound II

Synthetic route is as follows:

1)

2)

3)

1) the compound A2 of 181kg is added in a kettle, according to SOCl₂Molar ratio with compound A2 will for 1:1 SOCl₂It is added in reaction kettle, is warming up to 125 ± 5 DEG C, chlorine acylation is carried out under stirring condition, reaction time 12h is produced Raw HCl and SO₂Gas is pumped into collecting tank using vacuum, obtains compound B2 after reaction；

2) dry compound B2 is added in reaction vessel, is warming up to 75 ± 5 DEG C, predissolve and the NaF in water is added Enter in the reaction vessel, in 75 ± 5 DEG C of reaction 4-5h, after reaction dries product Compound C2；Wherein, compound B2 with The molar ratio of NaF is 1:2.5；

3) compound C2 obtained in step 2) is added in reaction vessel, is added into the reaction vessel a certain amount of HCl solution dissolves compound C2, is stirred to react, speed of agitator 1500rpm, reaction temperature be 90-100 DEG C, reaction until It when deposit-free, extracts reaction solution and supernatant is collected by centrifugation, the supernatant alkalimetric titration that collection is obtained, such as titration generate a large amount of mesh Product is marked, then stops reacting.

Compound II 129.1kg is prepared through the above steps, the yield of compound I is 93%.

Embodiment 3

Synthesize compound III

Synthetic route is as follows:

1)

2)

3)

1) compound A-13 of 211kg is added in a kettle, according to SOCl₂Molar ratio with compound A-13 will for 1:1 SOCl₂It is added in reaction kettle, is warming up to 125 ± 5 DEG C, chlorine acylation is carried out under stirring condition, reaction time 12h is produced Raw HCl and SO₂Gas is pumped into collecting tank using vacuum, obtains compound B3 after reaction；

2) dry compound B3 is added in reaction vessel, is warming up to 75 ± 5 DEG C, predissolve and the NaF in water is added Enter in the reaction vessel, in 75 ± 5 DEG C of reaction 2-3h, after reaction dries product Compound C3；Wherein, compound B3 with The molar ratio of NaF is 1:1.8；

3) compound C3 obtained in step 2) is added in reaction vessel, is added into the reaction vessel a certain amount of HCl solution dissolves compound C3, is stirred to react, speed of agitator 1500rpm, reaction temperature be 90-100 DEG C, reaction until It when deposit-free, extracts reaction solution and supernatant is collected by centrifugation, the supernatant alkalimetric titration that collection is obtained, such as titration generate a large amount of mesh Product is marked, then stops reacting.

Compound III 155.3kg is prepared through the above steps, the yield of compound I is 91.8%.

Embodiment 4

Synthesize compound IV

Synthetic route is as follows:

1)

2)

3)

1) the compound A4 of 197kg is added in a kettle, according to SOCl₂Molar ratio with compound A4 will for 1:1 SOCl₂It is added in reaction kettle, is warming up to 125 ± 5 DEG C, chlorine acylation is carried out under stirring condition, reaction time 12h is produced Raw HCl and SO₂Gas is pumped into collecting tank using vacuum, obtains compound B4 after reaction；

2) dry compound B4 is added in reaction vessel, is warming up to 75 ± 5 DEG C, predissolve and the NaF in water is added Enter in the reaction vessel, in 75 ± 5 DEG C of reaction 0.5-1h, after reaction dries product Compound C4；Wherein, compound B4 Molar ratio with NaF is 1:1.2；

3) compound C4 obtained in step 2) is added in reaction vessel, is added into the reaction vessel a certain amount of HCl solution dissolves compound C4, is stirred to react, speed of agitator 1500rpm, reaction temperature be 90-100 DEG C, reaction until It when deposit-free, extracts reaction solution and supernatant is collected by centrifugation, the supernatant alkalimetric titration that collection is obtained, such as titration generate a large amount of mesh Product is marked, then stops reacting.

Compound IV 150.2kg is prepared through the above steps, the yield of compound I is 95.7%.

Embodiment 5

Synthesize compound V

Synthetic route is as follows:

1)

2)

3)

1) compound A-45 of 459kg is added in a kettle, according to SOCl₂Molar ratio with compound A-45 will for 1:1 SOCl₂It is added in reaction kettle, is warming up to 125 ± 5 DEG C, chlorine acylation is carried out under stirring condition, reaction time 12h is produced Raw HCl and SO₂Gas is pumped into collecting tank using vacuum, obtains compound B5 after reaction；

2) dry compound B5 is added in reaction vessel, is warming up to 75 ± 5 DEG C, predissolve and the NaF in water is added Enter in the reaction vessel, in 75 ± 5 DEG C of reaction 5-6h, after reaction dries product Compound C5；Wherein, compound B5 with The molar ratio of NaF is 1:2.8；

3) compound C5 obtained in step 2) is added in reaction vessel, is added into the reaction vessel a certain amount of HCl solution dissolves compound C5, is stirred to react, speed of agitator 1500rpm, reaction temperature be 90-100 DEG C, reaction until It when deposit-free, extracts reaction solution and supernatant is collected by centrifugation, the supernatant alkalimetric titration that collection is obtained, such as titration generate a large amount of mesh Product is marked, then stops reacting.

Compound V 390kg is prepared through the above steps, the yield of compound I is 93.1%.

Embodiment 6

By the intermediate of embodiment 1A kind of red azo class reactive dye, the activity can be obtained by diazonium coupling Dyestuff has the compound of formula:

Performance such as the following table 1 of red reactive dyes prepared by the embodiment of the present invention 6.

The fastness ability of 1 dyestuff of table on the fabric

Experimental method:

Dyestuff on the fabric test referring to national standard by fastness ability: where the measurement of fastness to rubbing is referring to GB/ T3920-2008: " textile color stability test colour fastness to rubbing "；The measurement of washing fastness is referring to GB/T 5713-1997: " textile color stability test color fastness to water "；The measurement of sunlight fastness is referring to GB/T8426-1998: " textile color stability Test color fastness to light: daylight ".

Specific colouring method are as follows: coloration 3-5%, alkali number Na₂CO₃10g/L, electrolyte NaCl amount 50g/L, bath raio 1:30, 40 DEG C of temperature.Processed fabric is disseminated into 20min when room temperature in dye liquor, the NaCl of half amount is added, disseminates 20min, Be warming up to 40 DEG C be added the other half salt continue contaminate 20min, then be added half amount Na₂CO₃30min is contaminated, remainder one is added The Na of half amount₂CO₃It is dry after dye 30min.

The fastness ability of dyestuff on the fabric is measured referring to above-mentioned standard.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims

1. a kind of compound, which is characterized in that have the structure of logical formula (I):

Wherein, R₁、R₂、R₃、R₄And R₅In at least one be amino, remaining independently selected from H, halogen, hetero atom replace or not Substituted C_1-20Alkyl；

2. compound according to claim 1, which is characterized in that R₁、R₂、R₃、R₄And R₅In at least one be amino, It is remaining independently selected from H, halogen, C_1-10The C that alkyl or hetero atom replace_1-10Alkyl.

3. compound according to claim 1, which is characterized in that

R₁For amino；

4. compound according to claim 1, which is characterized in that

R₂For amino；

5. compound according to claim 1, which is characterized in that

R₃For amino；

6. compound according to claim 1, which is characterized in that the compound of the logical formula (I) is one of following:

7. the purposes of compound synthesis dyestuff described in any one of claims 1-6, which is characterized in that the compound is used as dye Expect the intermediate or meterial additive of intermediate, pharmaceutical intermediate, pesticide intermediate, photosensitive material.

8. the preparation method of compound described in any one of claims 1-6, characterized in that it comprises the following steps:

Wherein, R₁’、R₂’、R₃’、R₄' and R₅' at least one be amide groups or alkoxycarbonyl amido, remaining independently selected from H, the alkyl that halogen, alkyl or hetero atom replace；

C, so that the compound of logical formula (IV) is sloughed the acyl group of the amide groups or the alkoxy carbonyl group of the alkoxycarbonyl amido, obtain The compound of logical formula (I).

9. the preparation method of compound according to claim 8, which is characterized in that in the step a used in chlorination reaction Chlorinating agent be one of phosphorus trichloride, phosphorus pentachloride, thionyl chloride, sulfuryl chloride, chlorine, hydrogen chloride and phosgene or more Kind；

Preferably, the fluorization agent in the step b is NH₄F、LiF、NaF、KF、CsF、AgF、SbF₃、BrF₃、MnF₃、CuF、 (CH₃)₄NF and its hydrochlorate or (C₄H₉)₄One of NF and its ackd salt or a variety of.

10. the preparation method of compound according to claim 8, which is characterized in that if sloughing the acyl in the step c When the acyl group of amido, hydrolyze the compound of logical formula (IV) in acid, preferred 20-200 DEG C of hydrolysis temperature, hydrolysis time is preferred 0.1-48h；

If slough the alkoxy carbonyl group of the alkoxycarbonyl amido in the step c, make logical formula (IV) compound for catalysis hydrogenolysis, Acid cleavage or reduction.