JPH0576451B2 - - Google Patents
Info
- Publication number
- JPH0576451B2 JPH0576451B2 JP8726284A JP8726284A JPH0576451B2 JP H0576451 B2 JPH0576451 B2 JP H0576451B2 JP 8726284 A JP8726284 A JP 8726284A JP 8726284 A JP8726284 A JP 8726284A JP H0576451 B2 JPH0576451 B2 JP H0576451B2
- Authority
- JP
- Japan
- Prior art keywords
- azohydroperoxide
- reaction system
- reaction
- biphenyl compound
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- JXBDZNGGQLDTRU-UHFFFAOYSA-N (4-bromophenyl)-[hydroperoxy(phenyl)methyl]diazene Chemical compound C=1C=CC=CC=1C(OO)N=NC1=CC=C(Br)C=C1 JXBDZNGGQLDTRU-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- -1 biphenyl compound Chemical class 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- YXBIAYXZUDJVEB-UHFFFAOYSA-N 4-(3,4-dimethylphenyl)-1,2-dimethylbenzene Chemical group C1=C(C)C(C)=CC=C1C1=CC=C(C)C(C)=C1 YXBIAYXZUDJVEB-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Description
（産業上の利用分野）
本発明は、ビフエニル体の製造法に関するもの
である。
（従来の技術）
高分子化学原料等に利用されるビフエニルは、
高温、高圧下で、金属触媒を用い、ベンゼン、又
はその誘導体から得られているが、高温、高圧下
での反応なので、安全上、エネルギー消費の点、
及び高価な金属触媒を用いる点等問題が多い。
（発明の目的）
本発明の目的は、高温、高圧を必要としないビ
フエニル体の製造法を提供するものである。
（発明の構成）
本発明は、一般式
(Industrial Application Field) The present invention relates to a method for producing a biphenyl compound. (Conventional technology) Biphenyl, which is used as a polymer chemical raw material, is
It is obtained from benzene or its derivatives using a metal catalyst under high temperature and high pressure, but since the reaction is performed under high temperature and high pressure, there are concerns regarding safety and energy consumption.
There are many problems such as the use of expensive metal catalysts. (Object of the Invention) An object of the present invention is to provide a method for producing a biphenyl compound that does not require high temperature or high pressure. (Structure of the invention) The present invention is based on the general formula
【化】
（ここでR1はＨ、またはC1〜C4のアルキル基
またはアリール基である）
で示されるα−アゾヒドロペルオキシドおよび酸
化剤を芳香族炭化水素の基質に溶解させ、α−ア
ゾヒドロペルオキシドをラジカル分解するに必要
な光及び／又は熱を加え、α−アゾヒドロペルオ
キシドが消失してから、反応系内に酸素を導入す
ることを特徴とするビフエニル体の製造法であ
る。α−アゾヒドロペルオキシドは、例えば、対
応する芳香族ヒドラジンとアルデヒドを縮合さ
せ、更に酸化させて得られる。光照射は、高圧水
銀灯、メタルハライドランプ、螢光灯等で行うこ
とが出来、波長は一般に3000Å以上が好ましく、
更に、3200〜4200Åが好ましい。最適波長は、α
−アゾヒドロペルオキシドの種類によつて異な
る。光照射の場合温度は、任意の温度で良く、常
温で行われる。加熱は、基質の沸点以下の温度で
行われる。光照射、加熱によりα−アゾヒドロペ
ルオキシドがラジカル分解し、アリール（aryl）
ラジカルが発生する。α−アゾヒドロペルオキシ
ドの基質中での濃度は、10-3〜１モル／が使用
され、５×10-2モル／が好ましい。反応は、α
−アゾヒドロペルオキシドが消失するまで行わ
れ、光照射の場合10-2モル／のとき２〜10時間
程度である。濃度を薄くすると反応時間は短くて
良く、濃くすると長くなる。反応は、α−アゾヒ
ドロペルオキシドが分解し発生するラジカル（ア
リール（aryl）ラジカル）に対し不活性な気体、
例えばアルゴン、窒素、ヘリウム中で、又脱気下
で行われる。α−アゾヒドロペルオキシドが消失
してから、反応系内に酸素を導入する。純水な酸
素でも良く、空気でも良い。気泡として反応系内
に導入するのが好ましい。酸素の導入によつて、
副生成物として生成しているジヒドロビフエニル
体がビフエニル体に変わる。本発明は、大気圧で
反応が行われ、高温、高圧を必要とせず、又無
水、無触媒で行うことが出来る。
（発明の効果）
本発明は、α−アゾヒドロペルオキシドを芳香
族炭化水素基質中で、光照射及び／又は加熱後、
α−アゾヒドロペルオキシドが消失してから、反
応系内に酸素を導入することによりビフエニル体
を製造するものであり、高温、高圧を必要としな
いので、安全上も、エネルギー消費の点でも問題
がない。又、収率もよい。
実施例
オルソキシレン中に、[Chemical formula] (where R 1 is H or a C 1 to C 4 alkyl group or aryl group) α-azohydroperoxide and an oxidizing agent are dissolved in an aromatic hydrocarbon substrate, and α- This is a method for producing a biphenyl compound, which is characterized by applying light and/or heat necessary for radical decomposition of azohydroperoxide, and introducing oxygen into the reaction system after α-azohydroperoxide has disappeared. α-Azohydroperoxide can be obtained, for example, by condensing a corresponding aromatic hydrazine and an aldehyde and further oxidizing the condensate. Light irradiation can be performed using a high-pressure mercury lamp, metal halide lamp, fluorescent lamp, etc., and the wavelength is generally preferably 3000 Å or more.
Furthermore, 3200 to 4200 Å is preferable. The optimal wavelength is α
- Varies depending on the type of azohydroperoxide. In the case of light irradiation, the temperature may be any temperature, and the irradiation is performed at room temperature. Heating is performed at a temperature below the boiling point of the substrate. Upon light irradiation and heating, α-azohydroperoxide radically decomposes to form aryl.
Radicals are generated. The concentration of α-azohydroperoxide in the substrate used is 10 −3 to 1 mol/, preferably 5×10 −2 mol/. The reaction is α
- The treatment is carried out until the azohydroperoxide disappears, and in the case of light irradiation, it takes about 2 to 10 hours at 10 -2 mol/. The lower the concentration, the shorter the reaction time; the higher the concentration, the longer the reaction time. The reaction is carried out using a gas that is inert to the radicals (aryl radicals) generated when α-azohydroperoxide decomposes,
For example, it is carried out in argon, nitrogen, helium or under degassing. After α-azohydroperoxide has disappeared, oxygen is introduced into the reaction system. Pure water oxygen or air may be used. It is preferable to introduce it into the reaction system as bubbles. By introducing oxygen,
The dihydrobiphenyl compound produced as a by-product turns into a biphenyl compound. In the present invention, the reaction is carried out at atmospheric pressure, does not require high temperature or high pressure, and can be carried out without anhydride or catalyst. (Effects of the Invention) The present invention provides a method for preparing α-azohydroperoxide in an aromatic hydrocarbon substrate after light irradiation and/or heating.
The biphenyl compound is produced by introducing oxygen into the reaction system after α-azohydroperoxide has disappeared, and since high temperature and pressure are not required, there are no problems in terms of safety or energy consumption. do not have. Moreover, the yield is also good. Example In ortho-xylene,
【化】
で示されるα−アゾヒドロペルオキシドを10-2
Ｍ／、溶解した溶液を、アルゴン気流下で、高
圧水銀灯にてパイレツクスガラスを通して６時
間、室温で外部光照射した後、反応系内に２時間
酸素の散気を行い、３，４，3′，4′テトラメチル
ビフエニルを得た。収率（α−アゾヒドロペルオ
キシドの量に対して）は80％であつた。α-Azohydroperoxide represented by
After irradiating the dissolved solution with external light at room temperature for 6 hours through a Pyrex glass using a high-pressure mercury lamp under an argon stream, oxygen was diffused into the reaction system for 2 hours, and 3,4,3 ',4'tetramethylbiphenyl was obtained. The yield (based on the amount of α-azohydroperoxide) was 80%.
Claims (1)
またはアリール基である） で示されるα−アゾヒドロペルオキシドおよび酸
化剤を芳香族炭化水素の基質に溶解させ、ついで
前記α−アゾヒドロペルオキシドをラジカル分解
するに必要な光および／または熱を加え、その後
反応系内に酸素を導入することを特徴とするビフ
エニル体の製造法。[Claims] 1. α-Azohydroperoxide represented by the general formula [Chemical Formula] (where R 1 is H, or a C 1 to C 4 alkyl group or an aryl group) and an oxidizing agent are aromatic carbonized. 1. A method for producing a biphenyl compound, which comprises dissolving the α-azohydroperoxide in a hydrogen substrate, applying light and/or heat necessary for radical decomposition of the α-azohydroperoxide, and then introducing oxygen into the reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8726284A JPS60228428A (en) | 1984-04-27 | 1984-04-27 | Production of biphenyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8726284A JPS60228428A (en) | 1984-04-27 | 1984-04-27 | Production of biphenyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60228428A JPS60228428A (en) | 1985-11-13 |
| JPH0576451B2 true JPH0576451B2 (en) | 1993-10-22 |
Family
ID=13909858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8726284A Granted JPS60228428A (en) | 1984-04-27 | 1984-04-27 | Production of biphenyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60228428A (en) |
-
1984
- 1984-04-27 JP JP8726284A patent/JPS60228428A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60228428A (en) | 1985-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| BR9307200A (en) | Process for the purification of inert gases | |
| KR910011764A (en) | Method for producing α-hydroxyisobutyric acid amide | |
| JP2761761B2 (en) | Industrial production of aqueous solutions of glyoxylic acid | |
| KR920021483A (en) | Process for preparing polycarboxylic acid and derivatives thereof | |
| JPH0576451B2 (en) | ||
| US5527956A (en) | Process for the oxidation of aromatic methyl groups | |
| Schmitt et al. | Synthesis of 4, 6-dinitroresorcinol | |
| SU1685933A1 (en) | Chlorohydrate of 1-methyl-2-phenylthiomethyl-3-carboethoxy-4 -dimethylaminomethyl-5-oxy-6-bromoindole having antivirus action and method for obtaining it | |
| JPH0576450B2 (en) | ||
| JP2533596B2 (en) | Hydrogen peroxide production method | |
| JPS61158949A (en) | Production of 2-(4'-amylbenzoyl)benzoic acid mixture | |
| JP2997981B2 (en) | Method for producing 5-amino-4-oxo-2-pentenoic acid having protected amino group | |
| RU2036138C1 (en) | Method for enriching mixtures of diamonds and graphite or amorphous carbon with diamonds | |
| JP3257371B2 (en) | Method for producing 5-phthalimido-4-oxopentenoic acid or its pyridine salt | |
| JPS60228426A (en) | Production of biphenyl | |
| JPS5940151B2 (en) | Method for producing 1-phthalazinone | |
| JPH0426671A (en) | Purification of cumene hydroperoxide solution | |
| JPS6351352A (en) | Production of dichloroacetyl chloride | |
| CN118026832A (en) | Method for preparing halogenated anthraquinone compounds in one step | |
| JPS59163339A (en) | Production of acetic acid | |
| JPS5823858B2 (en) | Process for producing 2,3,5-trimethyl-para-benzoquinone | |
| JPS61103851A (en) | Production of benzophenone polycarboxylic acid | |
| JPH0474145A (en) | Production of phenol compound | |
| JPS6127927A (en) | Direct introduction of trifluoromethyl group to aromatic compound by photo-reaction | |
| JPS58154530A (en) | Preparation of halogenated hydroxylphenylacetic acid |