JPS6317819B2 - - Google Patents
Info
- Publication number
- JPS6317819B2 JPS6317819B2 JP59265346A JP26534684A JPS6317819B2 JP S6317819 B2 JPS6317819 B2 JP S6317819B2 JP 59265346 A JP59265346 A JP 59265346A JP 26534684 A JP26534684 A JP 26534684A JP S6317819 B2 JPS6317819 B2 JP S6317819B2
- Authority
- JP
- Japan
- Prior art keywords
- ammonia
- dibromobenzene
- diaminobenzene
- water
- pressure
- 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
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 20
- 239000005749 Copper compound Substances 0.000 claims description 9
- 150000001880 copper compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 6
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 5
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RRHNGIRRWDWWQQ-UHFFFAOYSA-N n-iodoaniline Chemical compound INC1=CC=CC=C1 RRHNGIRRWDWWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 2
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- CHHFZZHDXWPJKP-UHFFFAOYSA-N [N+](=[N-])=C1CC=CC=C1.[N+](=O)(O)[O-] Chemical compound [N+](=[N-])=C1CC=CC=C1.[N+](=O)(O)[O-] CHHFZZHDXWPJKP-UHFFFAOYSA-N 0.000 description 2
- 229960001413 acetanilide Drugs 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical compound NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- MGIWDIMSTXWOCO-UHFFFAOYSA-N butanedioic acid;copper Chemical compound [Cu].OC(=O)CCC(O)=O MGIWDIMSTXWOCO-UHFFFAOYSA-N 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- -1 copper halides Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は合成繊維、染料、酸化防止剤などの原
料である１，４−ジアミノベンゼンの合成法に関
する。くわしくは、１，４−ジブロモベンゼンと
アンモニアより１，４−ジアミノベンゼンの製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for synthesizing 1,4-diaminobenzene, which is a raw material for synthetic fibers, dyes, antioxidants, and the like. Specifically, the present invention relates to a method for producing 1,4-diaminobenzene from 1,4-dibromobenzene and ammonia.
（従来の技術）
１，４−ジアミノベンゼンの製造方法としては
アニリンから出発し、硝酸ジアゾベンゼン、１，
３−ジフエニールトリアゼン、４−アミノアゾベ
ンゼンを経由して合成する方法（アミノアゾベン
ゼン法）（特開昭52−65230号公報、特開昭52−
142041号公報、特開昭55−94349号公報、特開昭
57−122047号公報）。１，４−ベンゼンジカルボ
ン酸又はその（ポリ）エステルより出発し、１，
４−ベンゼンジカルボキシアミドを経由して合成
する方法（ホフマン分解法）（特公昭52−65230号
公報、特公昭57−34256号公報、特公昭57−35705
号公報、特公昭57−45734号公報、特開昭59−
130243号公報）。アセトアニリドから出発して、
４−ニトロアニリンを経由して合成するニトロア
ニリン法〔カーク・オスマー編化学工業百科辞典
（Kirk−Othmer編Encyclopedia of Chemical
Technology）、第３版、２巻、313頁、365頁〕。
ニトロベンゼンより出発して４−アミノフエノー
ルを経由するアミノフエノール法〔カーク・オス
マー編、化学工業百科辞典（Kirk−Othmer編
Encyclopedia of Chemical Technology）、第３
版、２巻、371頁ならびに特開昭55−153751号公
報〕。ハイドロキノンのアミノ化によるハイドロ
キノン法（特開昭49−29176号公報）。アニリンと
アンモニアより合成する直接アミノ化法（米国特
許第3919155号明細書）。１，４−ジクロロベンゼ
ンとアンモニア水より合成するジクロロベンゼン
法（特開昭51−59824号公報、特開昭53−77023号
公報、特開昭56−16449号公報、特公昭56−40145
号公報、特公昭57−61263号公報）。４−ヨードア
ニリンとアンモニアより合成するヨードアニリン
法（米国特許第3975349号明細書）が知られてい
る。(Prior art) As a method for producing 1,4-diaminobenzene, starting from aniline, diazobenzene nitrate, 1,
Synthesis method via 3-diphenyltriazene and 4-aminoazobenzene (aminoazobenzene method) (JP-A-52-65230, JP-A-52-
Publication No. 142041, Japanese Patent Publication No. 55-94349, Japanese Patent Publication No. Sho 55-94349
57-122047). Starting from 1,4-benzenedicarboxylic acid or its (poly)ester, 1,
Synthesis method via 4-benzenedicarboxamide (Hoffmann decomposition method) (Japanese Patent Publication No. 1983-65230, Japanese Patent Publication No. 57-34256, Japanese Patent Publication No. 57-35705)
Publication No. 57-45734, Japanese Patent Publication No. 1987-45734
Publication No. 130243). Starting from acetanilide,
Nitroaniline method synthesized via 4-nitroaniline (Encyclopedia of Chemical Industry, edited by Kirk-Othmer)
Technology), 3rd edition, vol. 2, pp. 313, 365].
Aminophenol process starting from nitrobenzene and passing through 4-aminophenol [Kirk-Othmer ed., Chemical Industry Encyclopedia (Kirk-Othmer ed.)]
Encyclopedia of Chemical Technology), No. 3
Edition, vol. 2, p. 371 and Japanese Patent Application Laid-open No. 153751/1983]. Hydroquinone method by amination of hydroquinone (Japanese Unexamined Patent Publication No. 49-29176). Direct amination method synthesized from aniline and ammonia (US Pat. No. 3,919,155). Dichlorobenzene method synthesized from 1,4-dichlorobenzene and aqueous ammonia (JP-A-51-59824, JP-A-53-77023, JP-A-56-16449, JP-A-56-40145)
Publication No. 57-61263). An iodoaniline method (US Pat. No. 3,975,349) is known in which the iodoaniline is synthesized from 4-iodoaniline and ammonia.
（本発明が解決しようとする問題点）
上記の従来の技術を実施しようとすると、それ
ぞれ重大な問題点がある。アミノアゾベンゼン法
は工程が長い上、中間段階で生成する硝酸ジアゾ
ベンゼンは爆発し易く、危険である。ホフマン分
解法も工程が長く、固体の中間体を経由するの
で、精製など複雑な工程を必要とする。ニトロア
ニリン法は原料のアセトアニリドが高価である上
製造工程が長い。直接アミノ化法は苛酷な条件を
必要とする上、収率、選択率とも低く、実用化か
らは遠い。アミノフエノール法は前段の４−アミ
ノフエノール合成工程が複雑かつ高価な設備を必
要とする電解還元である上、中間体の４−アミノ
フエノールが不安定で取扱いがやつかいであり、
さらに、後段のアミノ化工程も高温・高圧という
厳しい条件下での１，４−ジアミノベンゼンの合
成であるためタール状の高沸点物質が副生し、
１，４−ジアミノベンゼンの精製を困難にする。
ハイドロキノン法は原料のハイドロキノンが高価
な上、高温・高圧という厳しい条件を必要とす
る。ヨードアニリン法は高価かつ腐食性の強いヨ
ウ化物を使う上、異性体が副生し精製が難しい。(Problems to be Solved by the Present Invention) When trying to implement the above-mentioned conventional techniques, there are serious problems. The aminoazobenzene method requires a long process, and the diazobenzene nitrate produced in the intermediate stage is easily explosive and dangerous. The Hoffmann decomposition method is also a long process and requires complex steps such as purification because it involves a solid intermediate. In the nitroaniline method, the raw material acetanilide is expensive and the manufacturing process is long. The direct amination method requires harsh conditions and has low yield and selectivity, and is far from practical use. In the aminophenol method, the first stage of 4-aminophenol synthesis step is electrolytic reduction that requires complicated and expensive equipment, and the intermediate 4-aminophenol is unstable and difficult to handle.
Furthermore, since the subsequent amination step involves synthesizing 1,4-diaminobenzene under severe conditions of high temperature and pressure, tar-like high-boiling substances are produced as by-products.
Makes purification of 1,4-diaminobenzene difficult.
In the hydroquinone method, the raw material hydroquinone is expensive and requires severe conditions such as high temperature and high pressure. The iodoaniline method uses expensive and highly corrosive iodide, and isomers are produced as by-products, making purification difficult.
ジクロロベンゼン法は原料段階の精製が容易で
あり、異性体の生成もないが、高温・高圧を必要
とし、タール状の高沸点物質の副生が多く、精製
が大変である。たとえば、特公昭57−61263号公
報によれば175℃より低い温度ではｐ−ジクロロ
ベンゼンとアンモニア水からは殆どｐ−フエニレ
ンジアミンが生成しないことを教示している。ま
た、特公昭56−40145号公報は芳香族ジハライド
（実施例はすべて芳香族ジクロライドである）と
アンモニアからの芳香族ジアミンの生成反応は
160℃以下では殆ど進行しないため、170ないし
240℃で実施すること、そのさい、芳香族ジアミ
ンに対し５〜７％の重質物が副生することを教示
している。 Although the dichlorobenzene method is easy to purify at the raw material stage and does not produce isomers, it requires high temperatures and pressures, produces many tar-like high-boiling substances as by-products, and is difficult to purify. For example, Japanese Patent Publication No. 57-61263 teaches that p-phenylenediamine is hardly produced from p-dichlorobenzene and aqueous ammonia at temperatures lower than 175°C. In addition, Japanese Patent Publication No. 56-40145 describes the reaction for producing aromatic diamines from aromatic dihalides (all examples are aromatic dichlorides) and ammonia.
It hardly progresses at temperatures below 160℃, so
It is taught that the process is carried out at 240°C, and that 5 to 7% of heavy substances based on the aromatic diamine are produced as by-products.
（問題点を解決するための手段）
本発明者等は１，４−ジアミノベンゼンの改良
された製造法を鋭意検討した結果、１，４−ジブ
ロモベンゼンとアンモニアを水ならびに銅化合物
の共存下、比較的低温度に加熱することにより
１，４−ジアミノベンゼンを高収率かつ選択性良
く合成できることを見出し、本発明を完成するに
至つた。(Means for Solving the Problems) As a result of intensive research into an improved method for producing 1,4-diaminobenzene, the present inventors discovered that 1,4-dibromobenzene and ammonia were mixed in the coexistence of water and a copper compound. The present inventors have discovered that 1,4-diaminobenzene can be synthesized in high yield and with good selectivity by heating to a relatively low temperature, and have completed the present invention.
すなわち、本発明は、１，４−ジブロモベンゼ
ンとアンモニアを水ならびに銅化合物の共存下、
１，４−ジブロモベンゼンの融点以上160℃以下
の温度に加熱することからなる１，４−ジアミノ
ベンゼンの製造法を提供する。 That is, the present invention provides 1,4-dibromobenzene and ammonia in the coexistence of water and a copper compound,
Provided is a method for producing 1,4-diaminobenzene, which comprises heating 1,4-dibromobenzene to a temperature above the melting point and below 160°C.
本発明の方法に用いる銅化合物は、クロロベン
ゼン類のアミノ化で使われる銅化合物であれば何
でも良い。例示すると臭化銅、塩化銅等のハロゲ
ン化銅、酸化銅、水酸化銅、サク酸銅等の有機酸
銅がある。銅化合物は一価、二価いずれの銅化合
物でも良いが一価の銅化合物が好ましい。銅化合
物の使用量は１，４−ジブロモベンゼン１グラム
モルに対し、銅原子換算0.001ないし0.2グラムア
トムが好ましい。 The copper compound used in the method of the present invention may be any copper compound used in the amination of chlorobenzenes. Examples include copper halides such as copper bromide and copper chloride, and organic acid copper such as copper oxide, copper hydroxide, and copper succinate. The copper compound may be either a monovalent or divalent copper compound, but a monovalent copper compound is preferred. The amount of the copper compound used is preferably 0.001 to 0.2 gram atom in terms of copper atom per gram mole of 1,4-dibromobenzene.
本発明の方法において水の使用量は１，４−ジ
ブロモベンゼンに対し0.15ないし30重量倍が好ま
しく、アンモニアの量は１，４−ジブロモベンゼ
ン１モルに対し２モル以上、好ましくは10モル以
上、反応条件下の水−アンモニア相でのアンモニ
アの濃度は28重量％以上が好ましい。 In the method of the present invention, the amount of water used is preferably 0.15 to 30 times the weight of 1,4-dibromobenzene, and the amount of ammonia is 2 mol or more, preferably 10 mol or more, per 1 mol of 1,4-dibromobenzene. The concentration of ammonia in the water-ammonia phase under reaction conditions is preferably 28% by weight or more.
本発明の方法において、加熱温度は１，４−ジ
ブロモベンゼンの融点以上160℃以下でなければ
ならない。加熱温度が１，４−ジブロモベンゼン
の融点未満では反応が遅過ぎ、160℃を超過する
と選択性が悪くなる。 In the method of the present invention, the heating temperature must be above the melting point of 1,4-dibromobenzene and below 160°C. If the heating temperature is below the melting point of 1,4-dibromobenzene, the reaction will be too slow, and if it exceeds 160°C, the selectivity will deteriorate.
（発明の効果）
本発明の方法は従来知られている方法より温和
な条件下で、高収率かつ高選択率で１，４−ジア
ミノベンゼンを含成する方法である。(Effects of the Invention) The method of the present invention is a method for containing 1,4-diaminobenzene in high yield and high selectivity under milder conditions than conventionally known methods.
（実施例） 以下、実施例により本発明を説明する。(Example) The present invention will be explained below with reference to Examples.
実施例 １
１，４−ジブロモベンゼン５ｇ、臭化第一銅
0.5ｇ、28重量％アンモニア水40mlを撹拌機付の
内容積200mlのステンレス製オートクレーブに仕
込み、さらに、オートクレーブを氷冷しながら、
アンモニアを３Kg／cm2Ｇの圧力まで追添した。こ
のオートクレーブを125℃に加熱したところ、圧
力は70Kg／cm2Ｇを示した。この時の水−アンモニ
ア相中のアンモニア濃度は70重量％であつた。こ
の温度に６時間保つた後、オートクレーブを降
圧・冷却した。反応液をガスクロマトグラフで分
析したところ、１，４−ジブロモベンゼンは100
％反応し、１，４−ジアミノベンゼンの収率は
100モル％であつた。１，４−ジアミノベンゼン
以外の生成物は認められなかつた。ガスクロマト
グラフは水素炎イオン化検出器付、分離カラムは
ポリエチレングリコール20Mの２ｍカラムを200
℃で用いた。Example 1 1,4-dibromobenzene 5g, cuprous bromide
Charge 0.5g, 40ml of 28% ammonia water into a 200ml stainless steel autoclave equipped with a stirrer, and cool the autoclave with ice.
Ammonia was added to a pressure of 3 Kg/cm 2 G. When this autoclave was heated to 125°C, the pressure was 70Kg/cm 2 G. The ammonia concentration in the water-ammonia phase at this time was 70% by weight. After maintaining this temperature for 6 hours, the autoclave was depressurized and cooled. When the reaction solution was analyzed by gas chromatography, it was found that 1,4-dibromobenzene was 100%
% reaction, the yield of 1,4-diaminobenzene is
It was 100 mol%. No products other than 1,4-diaminobenzene were observed. The gas chromatograph is equipped with a hydrogen flame ionization detector, and the separation column is a 2m column of 20M polyethylene glycol.
It was used at ℃.
反応条件下のアンモニア濃度は反応条件下での
圧力に基きランドルトーベルンシユタイン ツア
ーレンベルテ ウント フンクチオネン アウス
フイジーク ヒエミイ アストロノミイ ゲオフ
イジーク ウント テクニーク
（LANDOLTBO¨RNSTEIN ZAHLENWERTE
UND FUNKTIONEN AUS PHYSIK
CHEMIE ASTRONOMIE GEOPHYSIK
UND TECHNIK）７版 バンド（BAND）、
アイゲンシヤフテン デア マテリエ イン イ
ーレン アグレガツツンステンデン２ テイル
バンドタイルａ（EIGENSCHAFTEN DER
MATERIE IN IHREN
AGGREGATZUNSTA¨NDEN 2TEIL
BANDTEIL ａ）378頁を用いて求めた。 The ammonia concentration under the reaction conditions is based on the pressure under the reaction conditions.
UND FUNKTIONEN AUS PHYSIK
CHEMIE ASTRONOMIE GEOPHYSIK
UND TECHNIK) 7th edition Band (BAND),
Eigenschaften der Materie in Eeren Agregatsunstenden 2 Theil
Band tile a (EIGENSCHAFTEN DER
MATERIE IN IHREN
AGGREGATZUNSTA¨NDEN 2TEIL
BANDTEIL a) Calculated using page 378.
実施例 ２
実施例１と同じオートクレーブに１，４−ジブ
ロモベンゼン５ｇ、臭化第一銅0.2ｇ、28％アン
モニア水40mlを仕込み、氷冷しながら３Kg／cm2Ｇ
の圧力でアンモニアを追添した後、155℃に加熱
したところ85Kg／cm2Ｇの圧力を示した。この時の
水−アンモニア相のアンモニア濃度は60重量％で
あつた。155℃に４時間保持したのち、降圧・冷
却した。１，４−ジブロモベンゼンは100％変化
し、１，４−ジアミノベンゼンの収率はほゞ100
モル％であつた。１，４−ジアミノベンゼン以外
の生成物は認められなかつた。Example 2 5 g of 1,4-dibromobenzene, 0.2 g of cuprous bromide, and 40 ml of 28% ammonia water were placed in the same autoclave as in Example 1, and the mixture was heated to 3 Kg/cm 2 G while cooling on ice.
After adding ammonia at a pressure of 150° C., the mixture was heated to 155° C. and a pressure of 85 kg/cm 2 G was obtained. The ammonia concentration in the water-ammonia phase at this time was 60% by weight. After maintaining the temperature at 155°C for 4 hours, the pressure was lowered and the mixture was cooled. 1,4-dibromobenzene was converted by 100%, and the yield of 1,4-diaminobenzene was approximately 100%.
It was mol%. No products other than 1,4-diaminobenzene were observed.
実施例 ３
１，４−ジブロモベンゼン５ｇ、臭化第一銅１
ｇ、28％アンモニア水40mlをオートクレーブに仕
込み、アンモニアを追添後、100℃に加熱したと
ころ、圧力40Kg／cm2Ｇを示した。この時の水−ア
ンモニア相のアンモニア濃度は68重量％であつ
た。１，４−ジブロモベンゼンは98％変化し、
１，４−ジアミノベンゼンが86モル％の選択率で
得られた。主な副生物は４−アミノフエノールと
４−ブロモアニリンであつた。Example 3 5 g of 1,4-dibromobenzene, 1 cuprous bromide
When the autoclave was charged with 40 ml of 28% ammonia water and ammonia was added, the autoclave was heated to 100° C., and a pressure of 40 Kg/cm 2 G was obtained. The ammonia concentration in the water-ammonia phase at this time was 68% by weight. 1,4-dibromobenzene changed by 98%,
1,4-diaminobenzene was obtained with a selectivity of 86 mol%. The main by-products were 4-aminophenol and 4-bromoaniline.
実施例 ４
１，４−ジブロモベンゼン５ｇ、臭化第一銅１
ｇ、28％アンモニア水40mlをオートクレーブに仕
込み、アンモニアを追添し、140℃に加熱したと
ころ、圧力は57Kg／cm2Ｇであつた。この時の水−
アンモニア相のアンモニアの濃度は55重量％であ
つた。140℃に７時間保持したのち、降圧・冷却
した。１，４−ジブロモベンゼンの転化率は100
％、１，４−ジアミノベンゼンの収率は95モル％
であつた。主な副生物はアミノフエノールであつ
た。Example 4 5 g of 1,4-dibromobenzene, 1 cuprous bromide
When the autoclave was charged with 40 ml of 28% ammonia water, ammonia was added thereto, and the autoclave was heated to 140°C, the pressure was 57 kg/cm 2 G. Water at this time
The concentration of ammonia in the ammonia phase was 55% by weight. After being held at 140°C for 7 hours, the pressure was lowered and cooled. The conversion rate of 1,4-dibromobenzene is 100
%, yield of 1,4-diaminobenzene is 95 mol%
It was hot. The main by-product was aminophenol.
実施例 ５
１，４−ジブロモベンゼン５ｇ、臭化第二銅
1.1ｇ、28％アンモニア水40mlをオートクレーブ
に仕込み、アンモニアを追添した。145℃に加熱
したところ、圧力53Kg／cm2Ｇを示した。この時の
水−アンモニア相のアンモニア濃度は48重量％で
あつた。１，４−ジブロモベンゼンの転化率100
％、１，４−ジアミノベンゼンの収率は75モル％
であり、副生物は４−ブロモアニリン、４−アミ
ノフエノールならびに少量の樹脂量物であつた。Example 5 1,4-dibromobenzene 5g, cupric bromide
1.1 g and 40 ml of 28% ammonia water were placed in an autoclave, and ammonia was added. When heated to 145°C, a pressure of 53Kg/cm 2 G was exhibited. The ammonia concentration in the water-ammonia phase at this time was 48% by weight. Conversion rate of 1,4-dibromobenzene 100
%, the yield of 1,4-diaminobenzene is 75 mol%
The by-products were 4-bromoaniline, 4-aminophenol and a small amount of resin.
比較例 １
１，４−ジブロモベンゼン５ｇ、臭化第一銅１
ｇ、28％アンモニア水40mlをオートクレーブに仕
込み、190℃に加熱したところ、圧力は50Kg／cm2
Ｇを示した。190℃で４時間保持したのち降圧、
冷却した。１，４−ジブロモベンゼンは100％変
化し、１，４−ジアミノベンゼンの得率は10モル
％であつた。主な副生物はアニリンならびにフエ
ノールであつた。Comparative example 1 5 g of 1,4-dibromobenzene, 1 cuprous bromide
When 40ml of 28% ammonia water was placed in an autoclave and heated to 190℃, the pressure was 50Kg/cm 2
It showed G. After holding at 190℃ for 4 hours, the pressure was lowered.
Cooled. The conversion of 1,4-dibromobenzene was 100%, and the yield of 1,4-diaminobenzene was 10 mol%. The main by-products were aniline and phenol.
比較例 ２
１，４−ジクロロベンゼン５ｇ、臭化第１銅
0.2ｇ、28％アンモニア水40mlを内容積200mlのス
テンレス製オートクレーブに仕込み、オートクレ
ーブを水冷しながらアンモニアを追添したのち、
155℃に加熱した。圧力は、85Kg／cm2Ｇになつた。
この温度で４時間保持したのち、降圧冷却した。
１，４−ジアミノベンゼンの生成は、ごく微量で
あつた。Comparative example 2 1,4-dichlorobenzene 5g, cuprous bromide
0.2 g, 40 ml of 28% ammonia water was placed in a stainless steel autoclave with an internal volume of 200 ml, and after adding ammonia while cooling the autoclave with water,
Heated to 155°C. The pressure became 85Kg/cm 2 G.
After being maintained at this temperature for 4 hours, it was cooled under reduced pressure.
The amount of 1,4-diaminobenzene produced was extremely small.
Claims (1)
ならびに銅化合物の共存下、１，４−ジブロモベ
ンゼンの融点以上160℃以下に加熱することを特
徴とする１，４−ジアミノベンゼンの製造方法。1. A method for producing 1,4-diaminobenzene, which comprises heating 1,4-dibromobenzene and ammonia in the coexistence of water and a copper compound to a temperature above the melting point of 1,4-dibromobenzene and below 160°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59265346A JPS61143341A (en) | 1984-12-18 | 1984-12-18 | Production of 1,4-diaminobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59265346A JPS61143341A (en) | 1984-12-18 | 1984-12-18 | Production of 1,4-diaminobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61143341A JPS61143341A (en) | 1986-07-01 |
| JPS6317819B2 true JPS6317819B2 (en) | 1988-04-15 |
Family
ID=17415897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59265346A Granted JPS61143341A (en) | 1984-12-18 | 1984-12-18 | Production of 1,4-diaminobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61143341A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04142812A (en) * | 1990-10-04 | 1992-05-15 | Toshiba Corp | Phase locked loop circuit |
| CN103145563B (en) * | 2013-03-29 | 2014-06-18 | 中北大学 | Method for co-producing p-phenylenediamine and o-phenylenediamine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5377023A (en) * | 1976-12-17 | 1978-07-08 | Toyo Soda Mfg Co Ltd | Preparation of aromatic diamine |
-
1984
- 1984-12-18 JP JP59265346A patent/JPS61143341A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5377023A (en) * | 1976-12-17 | 1978-07-08 | Toyo Soda Mfg Co Ltd | Preparation of aromatic diamine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61143341A (en) | 1986-07-01 |
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