CN101538283B - Oxazine compound and preparation method thereof - Google Patents
Oxazine compound and preparation method thereof Download PDFInfo
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- CN101538283B CN101538283B CN200810001431.4A CN200810001431A CN101538283B CN 101538283 B CN101538283 B CN 101538283B CN 200810001431 A CN200810001431 A CN 200810001431A CN 101538283 B CN101538283 B CN 101538283B
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- 0 CC(*)*N(COC1=C2C=CC(C)(*)C=C1)C2P1(Oc(cccc2)c2-c2c1cccc2)=O Chemical compound CC(*)*N(COC1=C2C=CC(C)(*)C=C1)C2P1(Oc(cccc2)c2-c2c1cccc2)=O 0.000 description 4
- GWHJZXXIDMPWGX-UHFFFAOYSA-N Cc1cc(C)c(C)cc1 Chemical compound Cc1cc(C)c(C)cc1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
An oxazine compound has a structure represented by a formula (I) on the right, wherein n is 1 or 2, when n is 1, X is hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, CF3, OCF3, phenyl, halogen, phenoxy or C3 to C7 cycloalkyl, and when n is 2, x is a single bond or a formula (II) on the right in which a is an integer from 1 to 16 and Ar is aromatics; Y is a single bond or a formula (III) in which Z1 and Z2 are independently hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, CF3, phenyl, halogen, phenoxy or C3 to C7 cycloalkyl; R is hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, CF3, OCF3, phenyl, halogen, phenoxy or C3 to C7 cycloalkyl; and m is 1 or 2.
Description
Technical field
The invention relates to a kind of benzoxazine and preparation method thereof, and relate to a kind of oxazine compound and preparation method thereof especially.
Background technology
The benzoxazine (Benzoxazine) that developed recently goes out, also known as oxo nitrogen for benzocyclohexane, it is a kind of phenolic resin.But, benzoxazine is slightly different from traditional phenolic resin, after not needing to add the catalyst of strong acid, Unit heating when it has high glass transition temperature (Tg), high-module (Modulus), low rate of moisture absorption, good electrical properties, high residual volume (charyield), sclerosis can open loop sclerosis and sclerosis time the advantages such as volume change is almost nil when not producing by product and sclerosis.
At present, the most frequently used benzoxazine is B-m and B-a type.B-m synthetic method is synthesized by dihydroxyphenyl propane and formaldehyde and methylamine; And B-a synthetic method is synthesized by dihydroxyphenyl propane and formaldehyde and aniline.The synthesis difference method of B-m and B-a is as follows:
Diplomatic benzoxazine is by synthesized by dihydroxyphenyl propane, formaldehyde and monofunctional amine.If adopt difunctionality base amine, formaldehyde and mono-functional phenols synthesis benzoxazine, then can form the insolubles of high molecular.Its reason is-NCH
2the amido of OH meeting and aniline carries out condensation reaction, and-NCH
2hydrogen dehydration on OH meeting and aniline on ortho position or a position and form the insolubles of high molecular.Therefore, during with difunctionality base amine, formaldehyde and mono-functional phenols synthesis benzoxazine, have high molecular insolubles and produce, cause purity difference, the problems such as productive rate is low.
In addition, although benzoxazine and traditional resin-phase comparatively have preferably flame resistivity, the flame resistivity of benzoxazine is still not enough, and application is still subject to very large restriction.
Summary of the invention
The invention provides a kind of oxazine compound, it has higher resistance to combustion characteristic.
The invention provides a kind of preparation method of oxazine compound, it can avoid producing insolubles in the process of preparation.
The invention provides a kind of preparation method of oxazine compound, it can prepare highly purified oxazine compound.
The invention provides a kind of preparation method of oxazine compound, it has high yield.
The present invention proposes a kind of oxazine (oxazine) compound, and its structure is as shown in the formula shown in (I):
Formula (I)
Wherein n is 1 or 2.When n is 1, X is hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.When N is 2, X be singly-bound or
Wherein a is the integer of 1 to 16.Ar is
Y is
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.M is 1 or 2.
Described in the embodiment of the present invention, in above-mentioned oxazine compound, when n is 2, X is symmetry centre.
The present invention proposes a kind of preparation method of oxazine compound.The structure of this oxazine compound is as shown in the formula shown in (II):
Formula (II)
Wherein X is hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.Y is
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.M is 1 or 2.The preparation method of oxazine compound contacts for making following compounds
To form the structure of following formula (III):
Formula (III)
Wherein the definition of X, Y, R, m is as described in above formula (II), afterwards, then adds formaldehyde or trioxymethylene to be formed.
Described in the embodiment of the present invention, in the preparation method of above-mentioned oxazine compound, the formation method of the compound of formula (III) was formed with single phase, and simultaneously its step will
Three contacts mixing.
Described in the embodiment of the present invention, in the preparation method of above-mentioned oxazine compound, the formation method of formula (III) is formed with two benches, and its step first will
The two mixing contact, to form the structure of following formula (IV):
Formula (IV)
Afterwards, then add
The present invention proposes a kind of preparation method of oxazine compound, shown in the following formula V of structure of this oxazine compound:
Formula (V)
Wherein: X be singly-bound or
Wherein a is the integer of 1 to 16.Ar is
Y is
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.M is 1 or 2.The preparation method of this oxazine compound makes following compounds contact
To form following formula (VI)
Formula (VI)
Wherein the definition of X, Y, R, m is as described in above formula (V), afterwards, then adds formaldehyde or trioxymethylene to be formed.
Described in the embodiment of the present invention, in the preparation method of above-mentioned oxazine compound, the formation method of formula (VI) was formed with single phase, and its step is simultaneously by following compounds contact mixing
Described in the embodiment of the present invention, in the preparation method of above-mentioned oxazine compound, the formation method of formula (VI) is formed with two benches.Its step first following compounds is mixed
To form the structure of following formula (VII):
Formula (VII)
Wherein the definition of X, Y, R, m is as described in above formula (V), afterwards, then adds
The oxazine compound of the embodiment of the present invention has higher resistance to combustion characteristic.
The preparation method of the oxazine compound of the embodiment of the present invention can avoid producing insolubles in the process of preparation.
The preparation method of the oxazine compound of the embodiment of the present invention can prepare highly purified oxazine compound.
The preparation method of the oxazine compound of the embodiment of the present invention has high yield.
For above and other object of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and coordinate institute's accompanying drawings, be described in detail below.
Accompanying drawing explanation
The 1H-NMR figure that Figure 1A and Figure 1B is respectively the intermediate P-DDM-HB of experimental example 2 of the present invention schemes with 13C-NMR.
The 1H-NMR that Fig. 1 C and Fig. 1 D is respectively the product P-DDM-Bz of experimental example 2 of the present invention schemes to scheme with 13C-NMR.
The 1H-NMR that Fig. 2 A and Fig. 2 B is respectively the intermediate P-BAPP-HB of experimental example 3 of the present invention schemes to scheme with 13C-NMR.
The 1H-NMR that Fig. 2 C and Fig. 2 D is respectively the product P-BAPP-Bz of experimental example 3 of the present invention schemes to scheme with 13C-NMR.
Fig. 3 A is the intermediate C of experimental example 5 of the present invention
2the 1H-NMR figure of-HB.
Fig. 3 B is the intermediate P-C of experimental example 5 of the present invention
2the 1H-NMR figure of-HB.
Fig. 3 C is the product P-C of experimental example 5 of the present invention
2the 1H-NMR figure of-Bz.
Fig. 4 A is the intermediate C of experimental example 6 of the present invention
4the 1H-NMR figure of-HB.
Fig. 4 B is the intermediate P-C of experimental example 6 of the present invention
4the 1H-NMR figure of-HB.
Fig. 4 C is the product P-C of experimental example 6 of the present invention
4the 1H-NMR figure of-Bz.
Fig. 5 A is the intermediate C of experimental example 7 of the present invention
6the 1H-NMR figure of-HB.
Fig. 5 B is the intermediate P-C of experimental example 7 of the present invention
6the 1H-NMR figure of-HB.
Fig. 5 C is the product P-C of experimental example 7 of the present invention
6the 1H-NMR figure of-Bz.
Fig. 6 A is the intermediate C of experimental example 8 of the present invention
8the 1H-NMR figure of-HB.
Fig. 6 B is the intermediate P-C of experimental example 8 of the present invention
8the 1H-NMR figure of-HB.
Fig. 6 C is the product P-C of experimental example 8 of the present invention
8the 1H-NMR figure of-Bz.
Embodiment
The structure of oxazine of the present invention (oxazine) compound as shown in the formula shown in (I),
Formula (I)
In above formula (I), Y is
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.M is 1 or 2.
In above formula (I), n is 1 or 2.When n is 1, X is hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.When n is 2, X is symmetry centre, be such as singly-bound or
Wherein a is the integer of 1 to 16.Ar is aromatics, such as, be
The preparation method of oxazine (oxazine) compound of above formula (I) is by Benzaldehyde,2-hydroxy (2-hydroxybenzaldehyde, 2HB), amine and 9, assorted-10-phospho hetero phenanthrene-10-oxide compound (10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, the DOPO) contact of 10-dihydro-9-oxy is mixed to form the intermediate with following formula (II ') structure:
Formula (II ')
Wherein the definition of X, Y, R, m and n is as described in above formula (I).Afterwards, then make formed intermediate and formaldehyde or trioxymethylene to be formed.
In more detail, oxazine compound of the present invention can adopt two benches forming method or three stage forming methods to prepare.
When the n during the structure shown in above formula (I) is is 1, the structure of oxazine compound of the present invention is as shown in the formula shown in (II):
Formula (II)
Wherein X is hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.Y is
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.M is 1 or 2.
The method adopting two benches to carry out the compound of preparation formula (II) first makes following compounds contact
To form the intermediate with following formula (III) structure:
Formula (III)
Wherein the definition of X, Y, R, m is as described in above formula (II).Afterwards, then add formaldehyde or trioxymethylene to be formed.Its chemical equation is as follows:
First make with the method for the compound of three stage preparation formulas (II)
The two contact mixing, to form the intermediate with following formula (IV) structure:
Formula (IV)
Afterwards, then add
To form the intermediate with formula (III) structure:
Formula (III)
Wherein the definition of X, Y, R, m is as described in above formula (II).Afterwards, then add formaldehyde or trioxymethylene to be formed.Its chemical equation is as follows:
When the n during the structure shown in above formula (I) is is 2, shown in the following formula V of structure of oxazine compound of the present invention:
Formula (V)
Wherein X is symmetry centre, its can be singly-bound or
Wherein a is the integer of 1 to 16.Ar is
Y is
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen, phenoxy group or C
3-C
7cycloalkyl.M is 1 or 2.
The method adopting two benches to prepare the compound of formula V first makes following compounds contact
Wherein the definition of X, Y, R, m is as described in above formula (V), to form the intermediate with following formula (VI) structure
Formula (VI)
Afterwards, then add formaldehyde or trioxymethylene to be formed.Its chemical equation is as follows:
The method adopting for three stages prepared the compound of formula V first will
Contact hybrid reaction, to form the intermediate with following formula (VII) structure:
Formula (VII)
Wherein the definition of X, Y, R, m is as described in above formula (V), afterwards, then adds
To form the intermediate with formula (VI) structure
Formula (VI)
Its chemical equation is as follows:
Experimental example 1
The lower routine compound (P-Aniline-Bz, Bz:benzoxazine) of two-stage synthesis
P-Aniline-Bz
The step of two-stage synthesis P-Aniline-Bz can be divided into, the synthesis that the stage (I) is intermediate P-Aniline-HB; The synthesis that stage (II) is P-Aniline-Bz.
Its reaction formula is as follows:
Stage (I) is synthetic intermediate P-Aniline-HB, get aniline 11.1688 grams (120 milli mole), Benzaldehyde,2-hydroxy 14.6544 grams (120 milli mole), DOPO 25.9404 grams (120 milli mole), be added to containing 300 milliliters of dimethyl methylamine (dimethyl formamide, DMF), in reaction flask, stir 12 hours at room temperature.After having reacted, solution is poured into adularescent precipitate in saturated aqueous common salt to separate out.Filter, dry, obtain white powder 46.07g, productive rate is 89%.The synthesis that stage (II) is P-Aniline-Bz, is the product 12.402g (30 milli mole) formed in the stage of getting (I), is added in the haloform reaction bottle containing 200 milliliters, gets formalin.2.6775g (33 milli mole) drips in reaction flask, and stirred at ambient temperature 5 hours, makes temperature rise to reflux temperature, and Keep agitation 12 hours.Reacted rear rotatory evaporator (Rotary) to be drained by solvent, obtained white powder, productive rate is 100%.
Experimental example 2
The lower routine compound P-DDM-Bz (DDM:4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane) of two benches synthesis
When manufacturing P-DDM-Bz with two benches, the stage (I) is synthetic intermediate P-DDM-HB; Stage (II) is synthesis P-DDM-Bz.Its reaction equation is as follows:
Stage (I) is synthetic intermediate P-DDM-HB.Get 4,4 '-diaminodiphenylmethane (DDM) 11.8956 grams (60 milli mole), Benzaldehyde,2-hydroxy (2-hydroxybenzaldehyde, 2-HB) 14.6544 grams (120 milli mole), DOPO 25.94 grams (120 milli mole), be added in the reaction flask containing 300 milliliters of DMF.At room temperature Keep agitation 12 hours.Pour in water by solution after having reacted, adularescent precipitate is separated out.Filter, dry, obtain dark green powder 46.54g, productive rate is 92%.Its result is as Figure 1A, 1B.The 1H-NMR figure that Figure 1A and Figure 1B is respectively intermediate P-DDM-HB schemes with 13C-NMR.Due to phosphorus with connect the aliphatic carbon that phosphorus connects and be palm center (chiral center), so P-DDM-HB is stereoisomers (diastereomers), include two kinds of isomers (RR (or SS) configuration and RS (or SR) configuration).Therefore, the summit of spectrum occurs two groups.Can confirm that the P-DDM-HB structure of synthesizing is errorless by figure.
Stage (II) is synthesis P-DDM-Bz.Get P-DDM-HB 25.1646g (30 milli mole), be added in the reaction flask containing 200 milliliters of chloroforms, get formalin 5.3549g (66 milli mole) and drip in reaction flask.Stirred at ambient temperature 5 hours, rises to reflux temperature by temperature, and Keep agitation 12 hours.React rear rotatory evaporator solvent is drained, then dried with vacuum drying oven, obtain brown powder, productive rate 100%.Its result such as 1C figure schemes with 1D.Fig. 1 C and 1D is that the 1H-NMR figure of product P-DDM-Bz schemes with 13C-NMR.Due to phosphorus and and connect the aliphatic carbon that phosphorus connects and be palm center, so P-DDM-Bz is a stereoisomers, include two kinds of isomers (RR (or SS) configuration and RS (or SR) configuration).Therefore, the summit of spectrum occurs two groups.Can confirm that the P-DDM-Bz structure of synthesizing is errorless by figure.
Experimental example 3
The compound P-BAPP-BZ (BAPP:2,2 '-two [4-(4-amino-benzene oxygen) phenyl] propane, 2,2 '-Bis [4-(4-aminophenoxy) phenyl] propane) of two benches synthesis having structure
When manufacturing P-BAPP-BZ with two benches, the synthesis that the stage (I) is intermediate P-BAPP-HB;
The synthesis that stage (II) is monomer P-BAPP-BZ.Its reaction equation is as follows:
Stage (I) synthesizes for intermediate P-BAPP-HB, get 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] 24.6306 grams, propane (BAPP) (60 milli mole), 2-HB 14.6544 grams (120 milli mole), DOPO25.9404 gram (120 milli mole), be added in the reaction flask containing 300 milliliters of DMF.Stir 12 hours at room temperature.After having reacted, solution is poured in water, have Shen Dian to separate out.Filter, dry, obtain pale yellow powder 60.12g, productive rate is 95%.Its result is as shown in Fig. 2 A, 2B.Fig. 2 A and Fig. 2 B, the 1H-NMR figure being respectively intermediate P-BAPP-HB schemes with 13C-NMR.Due to phosphorus with connect the aliphatic carbon that phosphorus connects and be palm center, so P-BAPP-HB is stereoisomers, include two kinds of isomers (RR (or SS) configuration and RS (or SR) configuration).Therefore, the summit of spectrum occurs two groups.Can confirm that the P-BAPP-HB structure of synthesizing is errorless by figure.
Stage (II) synthon P-BAPP-BZ.Get P-BAPP-HB 21.021 grams (20 milli mole), be added in the reaction flask containing 150 milliliters of chloroforms, get formalin 3.57 grams (44 milli mole) and drip in reaction flask.Stirred at ambient temperature 5 hours, rises to reflux temperature by temperature, and Keep agitation 12 hours.Reacted rear rotatory evaporator to be drained by solvent, dry with vacuum drying oven, obtain yellow powder P-BAPP-Bz, productive rate is 100%.Its result is as shown in Fig. 2 C, 2D.Fig. 2 C and Fig. 2 D, is respectively 1H-NMR and the 13C-NMR figure of product P-BAPP-Bz.Due to phosphorus and and connect the aliphatic carbon that phosphorus connects and be palm center, so P-BAPP-Bz is stereoisomers, include two kinds of isomers (RR (or SS) configuration and RS (or SR) configuration), therefore, the summit of spectrum occurs two groups.Can confirm that the P-BAPP-Bz structure of synthesizing is errorless by figure.
Experimental example 4
The lower routine compound P-DDS-Bz (DDS:4,4 '-diaminodiphenylsulfone(DDS), 4,4 '-Diaminodiphenyl sulfone) of two benches synthesis
When manufacturing P-DDS-Bz with two benches, the synthesis that the stage (I) is intermediate P-DDS-HB; The synthesis that stage (II) is P-DDS-Bz.Its reaction equation is as follows:
Stage (I) is synthetic intermediate P-DDS-HB, get 4,4 '-diaminodiphenylsulfone(DDS) (DDS) 14.898 grams (60 milli mole), 2-HB 14.6544 grams (120 milli mole), DOPO 25.9404 grams (120 milli mole), be added in the reaction flask containing 300 milliliters of DMF, stir 12 hours at room temperature.Pour in saturated aqueous common salt by solution after having reacted, adularescent precipitate is separated out.Filter, dry, obtain white powder 44.97 grams, productive rate is 84%.Stage (II) is synthesis P-DDS-Bz, get P-DDS-HB 26.6658 grams (30 milli mole), be added in the haloform reaction bottle containing 200 milliliters, getting formalin 5.3549 grams (66 milli mole) drips in reaction flask, stirred at ambient temperature 5 hours, temperature is risen to reflux temperature, and Keep agitation 12 hours.Reacted rear rotatory evaporator to be drained by solvent, obtained white powder P-DDS-Bz, productive rate is 100%.
Embodiment 5:
Structure P-C shown in following with the synthesis of three stages
2-Bz
P-C is manufactured with three stages
2during-Bz, the stage (I) is intermediate C
2the synthesis of-HB; Stage (II) is intermediate P-C
2the synthesis of-HB; Stage (III) is monomer P-C
2the synthesis of-Bz.Its reaction equation is as follows:
Stage (I) is synthetic intermediate C
2-HB, gets 2-HB 20.32 grams (2 × 83.25 milli mole), quadrol (ethylenediamine) 5 grams (83.25 milli mole) is dissolved in 50 milliliters of DMF and is placed in three neck round-bottomed bottles and stirs, pass into nitrogen.Reaction has heat release slightly.Under room temperature, Keep agitation reacts 6 hours.Solution and precipitate add in deionized water separates out, and by yellow powder vacuum drying oven vacuum drying at 100 DEG C after air exhaust filtering, obtains yellow powder C
2-HB21.6273 gram, productive rate is 96.8%.Fusing point 127.67 DEG C.Its result as shown in Figure 3A.Fig. 3 A is intermediate C
2the 1H-NMR figure of-HB.The C synthesized can be confirmed by figure
2-HB structure is errorless.
Proceed stage (II) synthon P-C
2-HB, gets C
2-HB5 gram (18.65 milli mole) molten ethanol to 30 milliliters, is added in 100 milliliters of three-necked bottles.Getting DOPO 8.058 grams (18.65 × 2 milli mole) adds in three-necked bottle, at room temperature stirs, reacts 12 hours.Yellow powder is had to separate out.Solution is dripped in deionized water and have yellow powder to separate out.After air exhaust filtering, filter cake is dried to obtain pale yellow powder P-C
2-HB12.6214 gram, productive rate=96.7%.Its result as shown in Figure 3 B.Fig. 3 B is intermediate P-C
2the 1H-NMR figure of-HB.The P-C synthesized can be confirmed by figure
2-HB structure is errorless.
Proceed stage (III) synthon P-C again
2-Bz, gets P-C
2-HB5 gram (14.3 milli mole), molten in the chloroform of 10 milliliters, be added in 100 milliliters of three-necked bottles.Get formalin (37%) 1.16 gram (14.3 × 2 milli mole) to drip in three-necked bottle.First stir 1 hour under room temperature (35 DEG C), temperature is risen to reflux temperature, Keep agitation 10 hours.Faint yellow powder P-C is dried to obtain with rotatory evaporator
2-Bz.Its result as shown in Figure 3 C.Fig. 3 C is product P-C
2the 1H-NMR figure of-Bz.The P-C synthesized can be confirmed by figure
2-Bz structure is errorless.
Embodiment 6:
The compound P-C of three stages synthesis shown in having structure
4-Bz
P-C is manufactured with three stages
4during-Bz, the stage (I) is intermediate C
4the synthesis of-HB; Stage (II) is intermediate P-C
4the synthesis of-HB; Stage (III) is monomer P-C
4the synthesis of-Bz.Its reaction equation is as follows:
Stage (I) is synthetic intermediate C
4-HB, gets 2-HB 13.8515 grams (56.75 × 2 milli mole), Putriscine (Isosorbide-5-Nitrae-butanediamine) 5 grams (56.75 milli mole) is dissolved in 50 milliliters of DMF and is placed in three neck round-bottomed bottles and stirs, pass into nitrogen.Reaction has heat release slightly.Under room temperature, Keep agitation reacts and makes amount of precipitation reach maximum value in 6 hours.Solution and precipitate add in deionized water separates out, and by yellow powder vacuum drying oven vacuum drying at 70 DEG C after air exhaust filtering, obtain yellow powder 4-HB21.6273 gram, productive rate is 96.8%.Fusing point 91 DEG C.Its result as shown in Figure 4 A.Fig. 4 A is intermediate C
4the 1H-NMR figure of-HB.The C synthesized can be confirmed by figure
4-HB structure is errorless.
Proceed stage (II) synthon P-C
4-HB, gets C
4-HB5 gram (16.88 milli mole) molten ethanol to 30 milliliters, is added in 100 milliliters of three-necked bottles.Getting DOPO 7.302 grams (16.88 × 2 milli mole) adds in three-necked bottle, at room temperature stirs, reacts 12 hours.Yellow powder is had to separate out.Solution is dripped in deionized water and have yellow powder to separate out.After air exhaust filtering, filter cake is dried to obtain pale yellow powder P-C
4-HB11.8963g, productive rate=96.8%.Its result as shown in Figure 4 B.Fig. 4 B is intermediate P-C
4the 1H-NMR figure of-HB.The P-C synthesized can be confirmed by figure
4-HB structure is errorless.
Proceed stage (III) synthon P-C
4-Bz, gets P-C
4-HB5 gram (13.7 milli mole), molten in the chloroform of 100 milliliters, be added in 500 milliliters of three-necked bottles.Get formalin (37%) 1.11 gram (13.7 × 2 milli mole) to drip in three-necked bottle.First stir 1 hour under room temperature (35 DEG C), temperature is risen to reflux temperature, Keep agitation 10 hours.Yellow-white powder P-C is dried to obtain with rotatory evaporator
4-Bz.Shown in its result Fig. 4 C.Fig. 4 C is product P-C
4the 1H-NMR figure of-Bz, can be confirmed the P-C synthesized by figure
4-Bz structure is errorless.
Embodiment 7:
The compound P-C of three stages synthesis shown in having structure
6-Bz
P-C is manufactured with three stages
6during-B, the stage (I) is intermediate C
6the synthesis of-HB; Stage (II) is intermediate P-C
6the synthesis of-HB; Stage (III) is monomer P-C
6the synthesis of-Bz.Its reaction equation is as follows:
Stage (I) is synthetic intermediate C
6-HB, gets 2-HB20.32 gram (2 × 83.25 milli mole), 1,6-hexanediamine (1,6-hexanediamine) 5 grams (83.25 milli mole) and is dissolved in 50 milliliters of DMF and is placed in three neck round-bottomed bottles and stirs, pass into nitrogen.There is yellow powder to separate out, and have heat release slightly.Under room temperature, Keep agitation reacts 6 hours.Solution and precipitate add in deionized water separates out, and by yellow powder vacuum drying oven vacuum drying at 100 DEG C after air exhaust filtering, obtains yellow powder C
6-HB 13.5465 grams, productive rate is 97%, fusing point 74.33 DEG C.Its result as shown in Figure 5A.Fig. 5 A is intermediate C
6the 1H-NMR figure of-HB, can be confirmed the C synthesized by figure
6-HB structure is errorless.
Proceed stage (II) synthon P ~ C
6-HB, gets C
6-HB5 gram (15.42 milli mole) molten ethanol to 30 milliliters, is added in 100 milliliters of three-necked bottles.Getting DOPO 6.662 grams (15.42 × 2 milli mole) adds in three-necked bottle, at room temperature stirs, reacts and have yellow powder to separate out after 12 hours.Solution is dripped in deionized water and have yellow powder to separate out.After air exhaust filtering, filter cake is dried to obtain pale yellow powder P-C
6-HB11.8963 gram, productive rate=96.8%.Its result as shown in Figure 5 B.Fig. 5 B is intermediate P-C
6the 1H-NMR figure of-HB.The P-C synthesized can be confirmed by figure
6-HB structure is errorless.
Continue and carry out stage (III) synthon P-C
6-Bz, gets P-C
6-HB5 gram (13.2 milli mole), molten in the chloroform of 100 milliliters, be added in 500 milliliters of three-necked bottles.Get formalin (37%) 1.11 gram (13.2 × 2 milli mole) to drip in three-necked bottle.First stir 1 hour under room temperature (35 DEG C), temperature is risen to reflux temperature, Keep agitation 10 hours.Yellow-white powder P-C is dried to obtain with rotatory evaporator
6-Bz.Its result as shown in Figure 5 C.Fig. 5 C is product P-C
6the 1H-NMR figure of-Bz.The P-C synthesized can be confirmed by figure
6-Bz structure is errorless.
Embodiment 8:
The synthesis of three stages has the compound P-C of following shown structure
8-Bz
P-C is manufactured with three stages
8during-Bz, the stage (I) is intermediate C
8the synthesis of-HB; Stage (II) is intermediate P-C
8the synthesis of-HB; Stage (III) is monomer P-C
8the synthesis of-Bz.Its reaction equation is as follows:
Stage (I) is synthetic intermediate C
8-HB, gets 2-HB20.32 gram (2 × 83.25 milli mole), 1,8-octamethylenediamine (1,8-octanediamine) 5 grams (83.25 milli mole) and is dissolved in 50 milliliters of DMF and is placed in three neck round-bottomed bottles and stirs, pass into nitrogen.There is yellow powder to separate out, and have heat release slightly.Under room temperature, Keep agitation reacts 6 hours.Solution and precipitate add in deionized water separates out, and by yellow powder vacuum drying oven vacuum drying at 100 DEG C after air exhaust filtering, obtains yellow powder C
8-HB 11.8216 grams, productive rate is 96.7%.Fusing point 76.83 DEG C.Its result as shown in Figure 6A.Fig. 6 A is intermediate C
8the 1H-NMR figure of-HB.The C synthesized can be confirmed by figure
8-HB structure is errorless.
Proceed stage (II) synthon P-C
8-HB, gets C
8-HB5 gram (14.2 milli mole) molten ethanol to 30 milliliters, is added in 100 milliliters of three-necked bottles.Getting DOPO 6.1353 grams (14.2 × 2 milli mole) adds in three-necked bottle, at room temperature stirs, reacts 12 hours.Yellow powder is had to separate out.Solution is dripped in deionized water and have yellow powder to separate out.After air exhaust filtering, filter cake is dried to obtain pale yellow powder P-C
8-HB10.4892g, productive rate=94.2%.Its result as shown in Figure 6B.Fig. 6 B is intermediate P-C
8the 1H-NMR figure of-HB.The P-C synthesized can be confirmed by figure
8-HB structure is errorless.
Afterwards, stage (III) synthon P-C is carried out
8-Bz, gets P-C
8-HB5 gram (12.7 milli mole), molten in the chloroform of 100 milliliters, be added in 500 milliliters of three-necked bottles.Get formalin (37%) 1.03 gram (12.7 × 2 milli mole) to drip in three-necked bottle.First stir 1 hour under room temperature (35 DEG C), temperature is risen to reflux temperature, Keep agitation 10 hours.Yellow-white powder P-C is dried to obtain with rotatory evaporator
8-Bz.Its result as shown in Figure 6 C.Fig. 6 C is product P-C
8the 1H-NMR figure of-Bz.The P-C synthesized can be confirmed by figure
8-Bz structure is errorless.
Above embodiment selects the electro amine of several different push-and-pulls to carry out synthesizing oxo nitrogen for benzocyclohexane, and wherein DDS has strong electron withdrawing group-SO
2-Ji, BAPP have and push away by force electronics base-O-, and aliphatics diamine DDM has and weakly pushes away electronics base CH
2base.But above experimental example is with the electro amine of several different push-and-pulls to represent the reflex action of all amine, it is only and principle of the present invention is described, and is not used to limit the present invention.The present invention's other amines all right, as aromatic amine (diamine, three amine, four amine) and aliphatics amine, obtain the oxazine compound with different structure via similar reaction.
From the embodiment of the invention described above, apply synthetic method of the present invention, can by the oxazine compound of difunctionality base amine, multifunctional amine or aliphatics diamine synthesis of high purity, high yield.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (8)
1. an oxazine compound, its structure is as shown in the formula shown in (I):
Formula (I)
Wherein:
N is 1 or 2, and
When n is 1, X is hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen or phenoxy group;
When N is 2, X is
or
Wherein:
A is the integer of 1 to 16; And
Ar is
or
Y is
or singly-bound
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3or halogen;
R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3or halogen; And
M is 1 or 2.
2. oxazine compound according to claim 1, when it is characterized in that wherein n is 2, X is symmetry centre.
3. a preparation method for oxazine compound, the structure of this oxazine compound is as shown in the formula shown in (II):
Formula (II)
Wherein:
X is hydrogen, C
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3, phenyl, halogen or phenoxy group;
Y is
or singly-bound
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3or halogen;
R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3or halogen; And
M is 1 or 2,
Its preparation method comprises:
Following compounds is contacted
To form the structure of following formula (III):
Formula (III)
Wherein the definition of X, Y, R, m is as described in above formula (II),
Afterwards, then add formaldehyde or trioxymethylene to be formed.
4. the preparation method of oxazine compound according to claim 3, it is characterized in that the formation method of the compound of its Chinese style (III) was formed with single phase, its step comprises:
To simultaneously
Three contacts mixing.
5. the preparation method of oxazine compound according to claim 3, it is characterized in that the formation method of its Chinese style (III) is formed with two benches, these steps comprise:
First will
The two contact mixing, to form the structure of following formula (IV):
Formula (IV)
and
Add again
6. a preparation method for oxazine compound, shown in the following formula V of structure of this oxazine compound:
Formula (V)
Wherein:
X is
or
Wherein:
A is the integer of 1 to 16; And
Ar is
or
Y is
or singly-bound
Wherein Z
1with Z
2be respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3or halogen;
R is respectively hydrogen, C separately
1-C
6alkyl, C
1-C
6alkoxyl group, CF
3, OCF
3or halogen; And
M is 1 or 2,
Its preparation method comprises:
Following compounds is contacted
and
To form following formula (VI)
Formula (VI)
Wherein the definition of X, Y, R, m is as described in above formula (V),
Afterwards, then add formaldehyde or trioxymethylene to be formed.
7. the preparation method of oxazine compound according to claim 6, it is characterized in that the formation method of its Chinese style (VI) was formed with single phase, its step comprises:
Simultaneously by following compounds contact mixing
and
8. the preparation method of oxazine compound according to claim 6, it is characterized in that the formation method of its Chinese style (VI) is formed with two benches, these steps comprise:
First following compounds is mixed
To form the structure of following formula (VII):
Formula (VII)
Wherein the definition of X, Y, R, m is as described in above formula (V),
Add again
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| CN107254141A (en) * | 2017-06-28 | 2017-10-17 | 盐城工业职业技术学院 | Fire retardant and terylene and fire retarding epoxide resin solidfied material and preparation method thereof |
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