CN105348038A - Synthetic method for 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds - Google Patents
Synthetic method for 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds Download PDFInfo
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Abstract
The invention relates to a synthetic method for 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds. The method employs o-nitro alkyl (alkoxyl) benzene as an initial raw material, 2,2'-dialkyl(alkoxyl) hydrazobenzene is prepared through catalysis hydrogenation in an alkaline environment, hydrochloric acid acidifying rearrangement is carried out, 4,4'-diamino-3,3'-dialkyl(alkoxyl) biphenyl is prepared, finally, a diazotization reaction is carried out and 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds are prepared. The synthetic method is advantaged by cheap and easily available raw materials, mild reaction conditions, simple operation, high safety coefficient, high yield and low cost.
Description
Technical field
The present invention relates to a kind of synthetic method of 4,4 '-two halogen substiuted-3,3 '-dioxane (oxygen) base biphenyl compound, belong to the field of chemical synthesis.
Background technology
4,4 '-two halogen substiuted-3,3 '-dioxane (oxygen) base biphenyl compound is the important fine chemicals intermediate of a class, be widely used in the middle of the synthesis of OLED, OPC, Other substrate materials, even pharmaceutical intermediate, in this compounds, the representational compound of most is 4,4 '-two halogen substiuted-3,3 '-dimethyl diphenyl.
Disclosed in document 4,4-bis-bromo-3, the synthetic method mainly following methods of 3 '-dimethyl diphenyl:
The where the shoe pinches of this kind of synthetic method is the synthesis of compd A and compd B: in the middle of the process of synthesis A; because 4-nitro-2-methyl bromobenzene contains the cause of nitro; it directly can not make grignard reagent; need when preparing grignard reagent to use grignard reagent displacement; and phenyl-magnesium-chloride grignard reagent itself is difficult to preparation; and this reaction needed is carried out under ultra-low temperature surroundings; conditional request is harsh; and yield low (20%); be difficult to large-scale production, cause expensive.
Summary of the invention
In view of 4,4 '-two halogen substiuted-3,3 '-dioxane (oxygen) base biphenyl compound tool has been widely used and many defects of existing synthetic method, our design studies is impelled to go out a kind of synthetic method of new simple possible, adopt present method synthesis 4,4 '-two halogen substiuted-3,3 '-dioxane (oxygen) base biphenyl compound, there is mild condition, simple to operate, yield is high, with low cost, starting material are easy to the advantages such as purchase, are applicable to laboratory and industrial scale operation.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of synthetic method of 4,4 '-two halogen substiuted-3,3 '-dioxane (oxygen) base biphenyl compound, comprising:
1) synthesis of intermediate E
Compound D is dissolved in alcoholic solvent, pour autoclave into, add 1,4-naphthoquinone, add the sodium hydroxide solution of mass concentration 50%, Sodium dodecylbenzene sulfonate and Pd/C catalyzer again, air three times in nitrogen replacement autoclave, then use hydrogen exchange three times, autoclave is sealed, open and stir, be heated to 30-60 DEG C, react under 0.6MPa condition, until autoclave pressure no longer changes, be cooled to 20-30 DEG C, discharging, leaches Pd/C catalyzer, filtrate layering, get organic layer, revolve and steam de-dry solvent, obtain intermediate E, reaction formula is as follows:
Wherein, R
1for the one in H, C1-C18 alkyl or C1-C18 alkoxyl group;
2) synthesis of intermediate F
By 1) intermediate E that obtains mixes with water, is warming up to 30-35 DEG C, drips the hydrochloric acid of mass concentration 35%, be warming up to 90-110 DEG C of insulation 2h, adjust pH=9-10, filter, use water wash filter cake, filter cake ethyl acetate heating for dissolving, filters, by de-for filtrate negative pressure dry, obtain crude product, crude product re crystallization from toluene, obtain intermediate F, reaction formula is as follows:
Wherein, R
1for the one in H, C1-C18 alkyl or C1-C18 alkoxyl group;
3) synthesis of product G1, G2 or G3
By 2) the intermediate F that obtains, the sulfuric acid of mass concentration 30%, acetonitrile and Glacial acetic acid mixing, be warming up to 70-80 DEG C, after insulation 0.5-1h, be cooled to-5-0 DEG C, in the sodium nitrite in aqueous solution of instillation mass concentration 40%, obtain diazo liquid, instill in acid reagent by diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, adds toluene, filters, filtrate layering, washing organic phase is to pH=7, and negative pressure takes off dry solvent, obtain crude product, add toluene and industrial alcohol recrystallization twice, obtain product G1, G2 or G3
Wherein, described acid reagent is the HX solution of CuX or the aqueous solution of KI, when acid reagent is the HX solution of CuX, intermediate F:CuX:HX=1mol:(2.1-2.5) mol:(5-6.5) mol, X=Br or Cl, when acid reagent is the aqueous solution of KI, intermediate F:KI=1mol:(2.1-2.5) mol, reaction formula is as follows
Wherein, R
1for the one in H, C1-C18 alkyl or C1-C18 alkoxyl group.
On the basis of technique scheme, the present invention can also do following improvement.
Further, 1) in, described alcoholic solvent is any one or a few the mixture in methyl alcohol, the ethanol of mass concentration 95%, Virahol, n-propyl alcohol, the trimethyl carbinol, propyl carbinol, tertiary amyl alcohol, the consumption of alcoholic solvent be the 5-8 of Compound D weight doubly.
Further, 1) in, the consumption of described 1,4-naphthoquinone is the 1%-1.5% of Compound D weight.
Further, 1) in, the weight of the sodium hydroxide solution of described mass concentration 50% is identical with alcoholic solvent consumption.
Further, 1) in, the consumption of described Sodium dodecylbenzene sulfonate is the 1%-1.6% of Compound D weight.
Further, 1) in, the consumption of described Pd/C catalyzer is the 1%-1.6% of Compound D weight, and containing Pd0.8wt% in Pd/C catalyzer, the Pd/C catalyzer leached can be reused.
Further, 2) in, in the hydrochloric acid of described intermediate E and mass concentration 35%, the mol ratio of HCl is 1mol:7mol.
Further, 3) in, the mol ratio of the Sodium Nitrite in the sodium nitrite in aqueous solution of described intermediate F and mass concentration 40% is 1mol:(1-1.2) mol.
Further, 3) in, the add-on of described toluene and industrial alcohol is equal to crude product weight.
Compare with existing synthetic method, the present invention possesses following advantage:
1, reaction conditions is gentle, without the need to ultrahigh-temperature, very low temperature reaction conditions, easy to implement, does not need anhydrous condition.
2, starting material are easy to get, low price, do not use the solvent that the prices such as tetrahydrofuran (THF) are higher, yield is high, except the first step uses Pd/C catalysis (and this step catalyzer can be recycled), other steps do not need expensive catalyzer, assist without the need to catalyzer.
3, final step adopts acetonitrile and Glacial acetic acid mixed solvent, and avoid the insoluble phenomenon of easily causing danger of diazonium salt, safety coefficient is high, and aftertreatment is simple, is easy to suitability for industrialized production.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 14, the synthesis of 4 '-dibromo (chlorine/iodine)-3,3 '-dimethyl diphenyl (G1-A ~ G1-C)
The synthesis of the dimethyl hydrogenated nitrogen benzide of 2,2'-(E1):
Raw material Ortho Nitro Toluene 102.8g (0.75mol) is dissolved in the ethanol of 700g mass concentration 95%, pour in autoclave, add 1.5g1, 4-naphthoquinones, add the sodium hydroxide solution of 700g mass concentration 50% again, 1.5g Sodium dodecylbenzene sulfonate and 1.5g contain the Pd/C catalyzer of Pd0.8wt%, in nitrogen replacement autoclave after air three times, use hydrogen exchange again three times, autoclave is sealed, open and stir, be heated to 30 DEG C, react under 0.6MPa condition, until autoclave pressure no longer changes, be cooled to 20-25 DEG C, discharging, leach Pd/C catalyzer reusable.Filtrate layering, gets organic layer, revolves and steams de-dry solvent, obtain the dimethyl hydrogenated nitrogen benzide of solid 2,2'-(E1) 74.2g, content 98.2%, yield 93.2%.
4, the synthesis of 4 '-diamino-3,3 '-dimethyl diphenyl (F1):
By raw material 2, the dimethyl hydrogenated nitrogen benzide of 2'-(E1) 74.2g mixes with water 315g, be warming up to 30-35 DEG C, drip the concentrated hydrochloric acid 252g of mass concentration 35%, drip to finish and be warming up to 90 DEG C of insulation 2h, pH=9-10 is adjusted in the aqueous sodium hydroxide solution alkalization adding 200g mass concentration 50%, filter, use 300g water wash, filter cake 371g ethyl acetate heating for dissolving, by de-for filtrate negative pressure dry after filtration, obtain crude product 58.2g, by crude product with 116.4g re crystallization from toluene once, obtain fine work, dry 4, 4 '-diamino-3, 3 '-dimethyl diphenyl (F1) 48.5g, content 99.5%, yield 65.3%.
4,4 '-two bromo-3, the synthesis of 3 '-dimethyl diphenyl (G1-A):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-dimethyl diphenyl (F1) 21.2g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 148.4g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, the sodium nitrite in aqueous solution of instillation 36.3g mass concentration 40%, obtained diazo liquid, (34.5gCuBr is dissolved in the Hydrogen bromide of 194.1g mass concentration 48%) in the HBr solution of CuBr will be instilled in diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, add 200g toluene, filter, filtrate layering, 300g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 31g, add 31g toluene and twice, 31g industrial alcohol recrystallization, obtain fine work 22.44g, content 99.5%, yield 66%.
Mp:120-125 DEG C;
1hNMR (400MHz, CDCl
3) δ: 7.68 (s, 2H), 7.54 (d, 2H), 7.34 (d, 2H);
13cNMR (100MHz, CDCl
3) δ: 140.6,138.5,133.0,132.0,127.1,124.0,24.1; HRMS (ESI): m/z calculated value: [M+H]
+: 339.9325.C
14h
12br
2test value: 339.9337.C
14h
11br
2; Ultimate analysis calculated value: C, 49.40; H, 3.53; Br, 47.00. test value: C, 49.25; H, 3.57; Br, 46.98.
4,4 '-two chloro-3, the synthesis of 3 '-dimethyl diphenyl (G1-B):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-dimethyl diphenyl (F1) 21.2g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 148.4g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, the sodium nitrite in aqueous solution of instillation 36.3g mass concentration 40%, obtained diazo liquid, (24.75gCuCl is dissolved in the hydrochloric acid of 67.8g mass concentration 35%) in the HCl solution of CuCl will be instilled in diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, add 200g toluene, filter, filtrate layering, 300g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 23g, add 23g toluene and 23g ethyl alcohol recrystallization twice, obtain fine work 17.1g, content 99.1%, yield 68.2%.
Mp:122-127 DEG C;
1hNMR (400MHz, CDCl
3) δ: 7.73 (s, 2H), 7.54 (d, 2H), 7.43 (d, 2H), 2.34 (s, 6H);
13cNMR (100MHz, CDCl
3) δ: 139.7,136.4,133.2,132.2,129.1,126.1,20.2; HRMS (ESI): m/z calculated value: [M+H]
+: 251.0235.C
14h
12br
2, test value: 251.0352.C
14h
11cl
2: ultimate analysis calculated value: C, 66.95; H, 4.82; Cl, 28.23. test value: C, 66.83; H, 4.86; Cl, 28.25.
4,4 '-two iodo-3, the synthesis of 3 '-dimethyl diphenyl (G1-C):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-dimethyl diphenyl (F1) 21.2g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 148.4g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, the sodium nitrite in aqueous solution of instillation 36.3g mass concentration 40%, obtained diazo liquid, (24.9gKI is dissolved in 150g water) in the aqueous solution of KI will be instilled in diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, add 200g toluene, filter, filtrate layering, 300g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 40g, add 40g toluene and twice, 40g industrial alcohol recrystallization, obtain fine work 30.4g, content 99.4%, yield 70%.
Mp:124-128 DEG C;
1hNMR (400MHz, CDCl
3) δ: 7.72 (d, 2H), 7.56 (s, 2H), 7.37 (d, 2H), 2.34 (s, 6H);
13cNMR (100MHz, CDCl
3) δ: 142.0,140.5,138.0,132.4,127.6,100.1,28.4; HRMS (ESI): m/z calculated value: [M+H]
+: 433.9305.C
14h
12i
2, test value: 433.9285.C
14h
11i
2: ultimate analysis calculated value: C, 38.74; H, 2.79; I, 58.47. test value: C, 38.68; H, 2.82; I, 58.46.
Embodiment 2:4, the synthesis of 4 '-dibromo (chlorine/iodine)-3,3 '-dimethoxy-biphenyl (G2-A ~ G2-C)
The synthesis of 2,2'-dimethoxy hydrazobenzene (E2):
Adjacent for raw material nitromethoxy benzene 114.8g (0.75mol) is dissolved in the ethanol of 600g mass concentration 95%, pour in autoclave, add 1.5g1, 4-naphthoquinones, add the sodium hydroxide solution of 600g mass concentration 50% again, 1.72g Sodium dodecylbenzene sulfonate and 1.72g contain the Pd/C catalyzer of Pd0.8wt%, air three times in nitrogen replacement autoclave, use hydrogen exchange again three times, autoclave is sealed, open and stir, be heated to 35 DEG C, react under 0.6MPa condition, until autoclave pressure no longer changes, be cooled to 20-25 DEG C, discharging, leach Pd/C catalyzer, reusable.Filtrate layering, gets organic layer, revolves and steams de-dry solvent, obtain solid 85.4g, content 98.6%, yield 93.3%.
4, the synthesis of 4 '-diamino-3,3 '-dimethoxy-biphenyl (F2):
By raw material 2, the dimethyl hydrogenated nitrogen benzide of 2'-(E2) 85.4g mixes with water 315g, intensification 30-35 DEG C, drip the hydrochloric acid 252g of mass concentration 35%, drip to finish and be warming up to 90 DEG C of insulation 2h, pH=9-10 is adjusted in the aqueous sodium hydroxide solution alkalization adding 200g mass concentration 50%, filters, uses 300g water wash, filter cake 371g ethyl acetate heating for dissolving, after filtration, filtrate negative pressure is de-dry, obtain crude product 66.6g, crude product with 199.8g re crystallization from toluene once, obtain fine work, dry to obtain 51.5g, content 99.3%, yield 60.3%.
4,4 '-two bromo-3, the synthesis of 3 '-dimethoxy-biphenyl (G2-A):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-dimethoxy-biphenyl (F2) 24.4g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 160g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, instillation 36.3g mass concentration 40% sodium nitrite in aqueous solution, obtained diazo liquid, (34.5gCuBr is dissolved in the Hydrogen bromide of 194.1g mass concentration 48%) in the HBr solution of CuBr will be instilled in diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, add 300g toluene, filter, filtrate layering, 350g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 28g, add 28g toluene and twice, 28g industrial alcohol recrystallization, obtain fine work 20.1g, content 99.5%, yield 71.78%.
Mp:129-132 DEG C;
1hNMR (400MHz, CDCl3) δ: 3.83 (s, 6H), 7.29 (d, 2H), 7.30 (d, 2H), 7.44 (d, 2H);
13cNMR (100MHz, CDCl3) δ: 155.1,144.8,130.3,121.6,121.5,113.1,55.3; HRMS (ESI): m/z calculated value: [M+H]
+: 284.1552.C
14h
12c
l2o
2, test value: 284.1528.C
14h
12c
l2o
2; Ultimate analysis calculated value: C, 59.33; H, 3.89; O, 11.30; Cl, 25.07. test value: C, 59.62; H, 3.84; O, 11.28; Cl, 25.10.
4,4 '-two chloro-3, the synthesis of 3 '-dimethoxy-biphenyl (G2-B):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-dimethoxy-biphenyl (F2) 24.4g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 160g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, instillation 36.3g mass concentration 40% sodium nitrite in aqueous solution, obtained diazo liquid, (24.75gCuCl is dissolved in the hydrochloric acid of 67.8g mass concentration 35%) in the hydrochloric acid soln of CuCl will be instilled in diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, add 300g toluene, filter, filtrate layering, 350g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 26g, add 26g toluene and twice, 26g industrial alcohol recrystallization, obtain fine work 22g, content 99.7%, yield 78.5%.
Mp:127-132 DEG C;
1hNMR (400MHz, CDCl3) δ: 7.44 (d, 2H), 7.30 (s, 2H), 7.29 (d, 2H), 3.83 (s, 6H);
13cNMR (100MHz, CDCl3) δ: 155.1,144.8,130.3,121.6,121.5,113.1,55.3; HRMS (ESI): m/z calculated value: [M+H]
+: 283.0218.C
14h
12c
l2o
2, test value 283.0189.C
14h
12c
l2o
2ultimate analysis calculated value: C, 59.39; H, 4.27; O, 11.30; Cl, 25.04. test value: C, 59.44; H, 4.36; O, 11.28; Cl, 25.08.
4,4 '-two iodo-3, the synthesis of 3 '-dimethoxy-biphenyl (G2-C):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-dimethoxy-biphenyl (F2) 24.4g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 160g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, instillation 36.3g mass concentration 40% sodium nitrite in aqueous solution, obtained diazo liquid, diazo liquid 0.5h is instilled in the aqueous solution of KI (24.9gKI is dissolved in 150g water), 30-40 DEG C of insulated and stirred 2h, add 300g toluene, filter, filtrate layering, 350g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 44g, add 44g toluene and 44g ethyl alcohol recrystallization twice, obtain fine work 37g, content 99.2%, yield 79.39%.
Mp:135-138 DEG C;
1hNMR (400MHz, CDCl3) δ: 7.73 (d, 2H), 7.13 (s, 2H), 7.12 (d, 2H), 3.83 (s, 6H);
13cNMR (100MHz, CDCl3) δ: 159.9,145.6,139.1,122.9,113.3,84.8,54.9; HRMS (ESI): m/z calculated value: [M+H]
+: 466.8875.C
14h
12i
2o
2test value 466.7875.C
14h
12i
2o
2; Ultimate analysis calculated value: C, 36.08; H, 2.60; O, 6.87; I, 54.46. test value: C, 36.10; H, 2.58; O, 6.79; Cl, 54.52.
Embodiment 3:4, the synthesis of 4 '-diiodo-(chlorine/bromine)-3,3 '-diethoxy biphenyl (G3A-G3C)
The synthesis of 2,2'-diethoxy hydrazobenzene (E3):
Raw material D3 o-ni troethoxybenzene 125.7g (0.75mol) is dissolved in the ethanol of 817.05g mass concentration 95%, pour in autoclave, add 1.5g1, 4-naphthoquinones, add the sodium hydroxide solution of 817.05g mass concentration 50% again, 1.9g Sodium dodecylbenzene sulfonate and 1.9g contain the Pd/C catalyzer of Pd0.8wt%, nitrogen replacement air three times, use hydrogen exchange again three times, autoclave is sealed, open and stir, be heated to 35 DEG C, react under 0.6MPa condition, until autoclave pressure no longer changes, be cooled to 20-25 DEG C, discharging, leach Pd/C catalyzer reusable.Filtrate layering, gets organic layer, revolves and steams de-dry solvent, obtain solid 2,2'-diethoxy hydrazobenzene (E3) 96g, content 98.8%, yield 94%.
4, the synthesis of 4 '-diamino-3,3 '-diethoxy biphenyl (F3):
By raw material 2, 2'-diethoxy hydrazobenzene (E3) 96g mixes with water 315g, be warming up to 30-35 DEG C, drip the concentrated hydrochloric acid 252g of mass concentration 35%, drip to finish and be warming up to 90 DEG C of insulation 2h, pH=9-10 is adjusted in the aqueous sodium hydroxide solution alkalization adding 200g mass concentration 50%, filter, use 300g water wash, filter cake 400g ethyl acetate heating for dissolving, by de-for filtrate negative pressure dry after filtration, obtain crude product 72.9g, crude product with 218.7g re crystallization from toluene once, obtain fine work 4, 4 '-diamino-3, 3 '-diethoxy biphenyl (F3), dry to obtain 53.7g, content 99.5%, yield 55.63%.
4,4 '-two bromo-3, the synthesis of 3 '-diethoxy biphenyl (G3-A):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-diethoxy biphenyl (F3) 27.2g (0.1mol) and 224g30%, 170g acetonitrile and the mixing of 160g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, obtained diazo liquid after instillation 36.3g40% sodium nitrite in aqueous solution, (34.5gCuBr is dissolved in the Hydrogen bromide of 194.1g mass concentration 48%) in the HBr solution of CuBr will be instilled in diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, add 300g toluene, filter, filtrate layering, 350g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 38.9g, add 38.9g toluene and twice, 38.9g industrial alcohol recrystallization, obtain fine work 28g, content 99.1%, yield 70%.
Mp:135-142 DEG C;
1hNMR (400MHz, CDCl3) δ: 7.55 (d, 2H), 7.25 (s, 2H), 7.09 (d, 2H), 4.09 (m, 4H), 1.32 (m, 6H);
13cNMR (100MHz, CDCl3) δ: 154.3,145.3,132.7,121.7,114.0,63.9,14.8; HRMS (ESI): m/z calculated value: [M+H]
+c
16h
16br
2o
2: 398.9542, test value: 398.9439.C
16h
16br
2o
2; Ultimate analysis calculated value: C, 48.03; H, 4.03; O, 8.01; Br, 39.94. test value: C, 48.04; H, 4.04; O, 7.99; Br, 39.92.
4,4 '-two chloro-3, the synthesis of 3 '-diethoxy biphenyl (G3-B):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-diethoxy biphenyl (F3) 27.2g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 160g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, instillation 36.3g mass concentration 40% sodium nitrite in aqueous solution, obtained diazo liquid, diazo liquid 0.5h is instilled in the hydrochloric acid soln of CuCl (24.75gCuCl is dissolved in the hydrochloric acid of 67.8g mass concentration 35%), 30-40 DEG C of insulated and stirred 2h, add 300g toluene, filter, filtrate layering, 350g water is added in organic phase, be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 47.94g, add 47.94g toluene and twice, 47.94g industrial alcohol recrystallization, obtain fine work 39.3g, content 99.5%, yield 79.54%.
Mp:138-142 DEG C;
1hNMR (400MHz, CDCl3) δ: 1.32 (m, 6H), 4.09 (m, 4H), 7.29 (d, 2H), 7.30 (s, 2H), 7.44 (d, 2H);
13cNMR (100MHz, CDCl3) δ: 151.9,144.4,129.9,121.6,120.9,113.2,64.1,14.8; HRMS (ESI): m/z calculated value: [M+H]+: 493.8542.C
16h
16c
l2o
2, test value: 493.8592.C
16h
16c
l2o
2ultimate analysis calculated value: C
16h
16c
l2o
2: C, 61.75; H, 5.18; O, 10.28; Cl, 22.78. test value: C, 61.72; H, 5.21; O, 10.26; Cl, 22.80.
4,4 '-two iodo-3, the synthesis of 3 '-diethoxy biphenyl (G3-C):
By raw material 4, 4 '-diamino-3, the sulfuric acid of 3 '-diethoxy biphenyl (F3) 27.2g (0.1mol) and 224g mass concentration 30%, 170g acetonitrile and the mixing of 160g Glacial acetic acid,-5-0 DEG C is cooled to after being warming up to 70-80 DEG C of insulation 0.5h salify, instillation 36.3g mass concentration 40% sodium nitrite in aqueous solution, obtained diazo liquid, (24.9gKI is dissolved in 124.5g water) in the aqueous solution of KI will be instilled in diazo liquid 0.5h, 300g toluene is added after 30-40 DEG C of insulated and stirred 2h, filter, filtrate layering, add 350g water in organic phase and be washed to pH=7, negative pressure takes off dry solvent, obtain crude product 47.94g, add 47.94g toluene and twice, 47.94g industrial alcohol recrystallization, obtain fine work 39.3g, content 99.5%, yield 79.54%.
Mp:130-135 DEG C;
1hNMR (400MHz, CDCl3) δ: 1.32 (m, 6H), 4.09 (m, 4H), 7.12 (d, 2H), 7.13 (s, 2H), 7.73 (d, 2H);
13cNMR (100MHz, CDCl3) δ: 156.7,145.2,138.7,122.2,113.4,84.9,63.7,14.8; HRMS (ESI): m/z calculated value: [M+H]
+: 493.8542, C
16h
16i
2o
2test value: 493.8592.C
16h
16i
2o
2ultimate analysis calculated value: C
16h
16i
2o
2: C, 38.89; H, 3.26; O, 6.48; I, 51.37. test value: C, 38.76; H, 3.29; O, 6.4; I, 51.35.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. one kind 4, the synthetic method of 4 '-two halogen substiuted-3,3 '-dioxane (oxygen) base biphenyl compound, is characterized in that, comprising:
1) synthesis of intermediate E
Compound D is dissolved in alcoholic solvent, pour autoclave into, add 1,4-naphthoquinone, add the sodium hydroxide solution of mass concentration 50%, Sodium dodecylbenzene sulfonate and Pd/C catalyzer again, air three times in nitrogen replacement autoclave, then use hydrogen exchange three times, autoclave is sealed, open and stir, be heated to 30-60 DEG C, react under 0.6MPa condition, until autoclave pressure no longer changes, be cooled to 20-30 DEG C, discharging, leaches Pd/C catalyzer, filtrate layering, get organic layer, revolve and steam de-dry solvent, obtain intermediate E, reaction formula is as follows:
Wherein, R
1for the one in H, C1-C18 alkyl or C1-C18 alkoxyl group;
2) synthesis of intermediate F
By 1) intermediate E that obtains mixes with water, is warming up to 30-35 DEG C, drips the hydrochloric acid of mass concentration 35%, be warming up to 90-110 DEG C of insulation 2h, adjust pH=9-10, filter, use water wash filter cake, filter cake ethyl acetate heating for dissolving, filters, by de-for filtrate negative pressure dry, obtain crude product, crude product re crystallization from toluene, obtain intermediate F, reaction formula is as follows:
Wherein, R
1for the one in H, C1-C18 alkyl or C1-C18 alkoxyl group;
3) synthesis of product G1, G2 or G3
By 2) the intermediate F that obtains, the sulfuric acid of mass concentration 30%, acetonitrile and Glacial acetic acid mixing, be warming up to 70-80 DEG C, after insulation 0.5-1h, be cooled to-5-0 DEG C, in the sodium nitrite in aqueous solution of instillation mass concentration 40%, obtain diazo liquid, instill in acid reagent by diazo liquid 0.5h, 30-40 DEG C of insulated and stirred 2h, adds toluene, filters, filtrate layering, washing organic phase is to pH=7, and negative pressure takes off dry solvent, obtain crude product, add toluene and industrial alcohol recrystallization twice, obtain product G1, G2 or G3
Wherein, described acid reagent is the HX solution of CuX or the aqueous solution of KI, when acid reagent is the HX solution of CuX, intermediate F:CuX:HX=1mol:(2.1-2.5) mol:(5-6.5) mol, X=Br or Cl, when acid reagent is the aqueous solution of KI, intermediate F:KI=1mol:(2.1-2.5) mol
Reaction formula is as follows,
Wherein, R
1for the one in H, C1-C18 alkyl or C1-C18 alkoxyl group.
2. synthetic method according to claim 1, it is characterized in that, 1) in, described alcoholic solvent is any one or a few the mixture in methyl alcohol, the ethanol of mass concentration 95%, Virahol, n-propyl alcohol, the trimethyl carbinol, propyl carbinol, tertiary amyl alcohol, the consumption of alcoholic solvent be the 5-8 of Compound D weight doubly.
3. synthetic method according to claim 1, is characterized in that, 1) in, the consumption of described 1,4-naphthoquinone is the 1%-1.5% of Compound D weight.
4. synthetic method according to claim 1, is characterized in that, 1) in, the weight of the sodium hydroxide solution of described mass concentration 50% is identical with alcoholic solvent consumption.
5. synthetic method according to claim 1, is characterized in that, 1) in, the consumption of described Sodium dodecylbenzene sulfonate is the 1%-1.6% of Compound D weight.
6. synthetic method according to claim 1, is characterized in that, 1) in, the consumption of described Pd/C catalyzer is the 1%-1.6% of Compound D weight, and containing Pd0.8wt% in Pd/C catalyzer, the Pd/C catalyzer leached can be reused.
7. synthetic method according to claim 1, is characterized in that, 2) in, in the hydrochloric acid of described intermediate E and mass concentration 35%, the mol ratio of HCl is 1mol:7mol.
8. synthetic method according to claim 1, is characterized in that, 3) in, the mol ratio of the Sodium Nitrite in the sodium nitrite in aqueous solution of described intermediate F and mass concentration 40% is 1mol:(1-1.2) mol.
9. synthetic method according to claim 1, is characterized in that, 3) in, the add-on of described toluene and industrial alcohol is equal to crude product weight.
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| CN108218711A (en) * | 2018-01-12 | 2018-06-29 | 浙江鼎龙科技有限公司 | A kind of preparation method of 3,3 ', 4,4 '-tetra-amino-biphenyl |
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| CN112110806A (en) * | 2020-09-10 | 2020-12-22 | 浙江永太科技股份有限公司 | Preparation method and intermediate of 1- (3, 5-dichloro-4-fluoro-phenyl) -2,2, 2-trifluoroacetone |
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| CN106496046A (en) * | 2016-09-28 | 2017-03-15 | 连云港泰盛化工有限公司 | The method that solvent-free catalytic hydrogenation produces aminoanisole |
| CN107324964A (en) * | 2017-06-22 | 2017-11-07 | 陕西师范大学 | A kind of synthetic method of biphenyl analog derivative |
| CN108218711A (en) * | 2018-01-12 | 2018-06-29 | 浙江鼎龙科技有限公司 | A kind of preparation method of 3,3 ', 4,4 '-tetra-amino-biphenyl |
| CN109232273A (en) * | 2018-10-23 | 2019-01-18 | 烟台海川化学制品有限公司 | The preparation method of bis- (trifluoromethyl) -4,4 '-benzidines of one kind 2,2 ' - |
| CN112110806A (en) * | 2020-09-10 | 2020-12-22 | 浙江永太科技股份有限公司 | Preparation method and intermediate of 1- (3, 5-dichloro-4-fluoro-phenyl) -2,2, 2-trifluoroacetone |
| CN112110806B (en) * | 2020-09-10 | 2022-11-15 | 浙江永太科技股份有限公司 | Preparation method and intermediate of 1- (3, 5-dichloro-4-fluoro-phenyl) -2, 2-trifluoroacetone |
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