EP0000519B1 - Procédé de préparation du dichloro-2,2'-hydrazobenzène - Google Patents

Procédé de préparation du dichloro-2,2'-hydrazobenzène Download PDF

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Publication number
EP0000519B1
EP0000519B1 EP78100394A EP78100394A EP0000519B1 EP 0000519 B1 EP0000519 B1 EP 0000519B1 EP 78100394 A EP78100394 A EP 78100394A EP 78100394 A EP78100394 A EP 78100394A EP 0000519 B1 EP0000519 B1 EP 0000519B1
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EP
European Patent Office
Prior art keywords
anthraquinone
reduction
nitrochlorobenzene
dichlorohydrazobenzene
catalyst
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
Application number
EP78100394A
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German (de)
English (en)
Other versions
EP0000519A1 (fr
Inventor
Siegfried Dr. Planker
Konrad Dr. Baessler
Otto Dr. Fuchs
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0000519A1 publication Critical patent/EP0000519A1/fr
Application granted granted Critical
Publication of EP0000519B1 publication Critical patent/EP0000519B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C241/02—Preparation of hydrazines

Definitions

  • the invention relates to a process for the preparation of 2,2'-dichlorohydrazobenzene by catalytic reduction of o-nitrochlorobenzene with hydrogen.
  • the temperature is between 40-100 ° C, preferably at 60 to 70 ° C, the hydrogen (over) pressure at about 0.4 to 7.8 bar (20-125 psi, abs.), Preferably about 0.75 to 1.8 bar (25-40 psi, abs.).
  • the hydrogen (over) pressure at about 0.4 to 7.8 bar (20-125 psi, abs.), Preferably about 0.75 to 1.8 bar (25-40 psi, abs.).
  • naphthalene derivatives such as naphthoquinone- (1,4) or 2,3-dichloro-naphthoquinone- (1,4) are added to the reaction mixture.
  • the yields of 2,2'-dichlorohydrazobenzene obtained in this way vary between 80 and 90%, and the chlorine elimination is said to be low.
  • anthraquinone preferably hydroxyanthraquinones, for example ⁇ -hydroxyanthraquinone or 2,6-dihydroxyanthraquinone, can be added.
  • the noble metal catalysts can be recycled very often when the anthraquinone derivatives are used, without suffering a drop in activity. Even after e.g. Ten times the precious metal catalysts are used, constant yields are obtained in the same reduction time as in the starting batch.
  • the anthraquinone derivatives accelerate the reduction of the individual reaction stages, in particular the azoxy and azo stage, much more strongly than naphthoquinone compounds, so that a lower temperature is made possible during the entire reaction time, and even shorter reaction times are achieved than when using the known naphthoquinones.
  • Another advantage is that e.g. the ß-hydroxyanthraquinone after the reduction from the aqueous mother liquor by setting a pH of 3 to 4 can be precipitated practically quantitatively and can be reused several times without purification, while the 2-hydroxy-3-chloro-naphthoquinone- (1,4) (formed during the reduction from 2,3-dichloronaphthoquinone (1,4)) has to be eliminated by a complex wastewater treatment.
  • the amount of anthraquinones used is small, it is lower than that of the naphthoquinone derivatives.
  • a weight ratio of ß-hydroxyanthraquinone to o-chloronitrobenzene of 0.003 to 0.008, in particular 0.004: 1 is sufficient to evenly reduce the dichlorazoxybenzene which occurs as an intermediate via the dichlorazobenzene through to the hydrazo compound, while of 2,3-dichloronaphthoquinone- (1,4) twice the amount is necessary in order to achieve comparable results at least when the noble metal catalysts are used for the first time.
  • a 16 to 25% sodium hydroxide solution is used as the reaction medium in such an amount that, after the reaction has ended, a 10 to 15% sodium hydroxide solution is produced by the water of reaction formed concentration arises.
  • anthraquinones show advantages over the naphthoquinones. While the best results are achieved with naphthoquinone with a 16% sodium hydroxide solution in a weight ratio of o-nitrochlorobenzene to NaOH (100%) such as 1: 0.095, the anthraquinones allow an increase in the NaOH concentration up to 25% and a lower use of sodium hydroxide solution in a weight ratio of o-nitrochlorobenzene to NaOH (100%) such as 1:: 0.071, without slowing down the reaction rate.
  • the use of an approx. 25% NaOH means an improvement in the space yield of approx. 20% compared to a 16% NaOH according to the above weight ratios.
  • the reaction temperature is preferably between 55 to 60 ° C., the hydrogen pressure preferably between 1 to 6 bar, it being advantageous to let the pressure rise slowly within the specified limit values during the reduction.
  • the reduction is carried out particularly advantageously in such a way that o-nitrochlorobenzene, aqueous sodium hydroxide solution, the anthraquinone derivative, e.g. ß-Hydroxyanthraquinone, solvent, an emulsifier and a noble metal catalyst are filled into a conventional autoclave and, after the air has been displaced, heated with nitrogen while stirring. The nitrogen is replaced by hydrogen and hydrogen is pressed on until there is no more pressure drop. The desired reaction temperature is maintained by external cooling or heating.
  • the catalyst is filtered off under nitrogen and returned to the next reduction batch without purification, it being possible to use it at least ten times.
  • the o-chloroaniline is washed out with dilute hydrochloric acid, the solvent is distilled off and the hydrazo compound is dried. Since the product is obtained in sufficient purity, the organic phase can also be fed directly to the rearrangement with mineral acids to give 3,3'-dichlorobenzidine.
  • the process according to the invention thus makes it possible to produce 2,2'-dichlorohydrazobenzene in a particularly economical manner by catalytic reduction of o-nitrochlorobenzene in the presence of anthraquinones in high yields and in a reproducible manner.
  • the advantages of the method according to the invention are explained in more detail in the following examples. The percentages relate to the weight, unless stated otherwise.
  • the reaction mixture After the air has been displaced in a closed autoclave with nitrogen, the reaction mixture is heated to 60 ° C. with stirring and hydrogen is injected to 3 bar. Depending on the hydrogen uptake, the hydrogen pressure is increased to 6 bar by the end of the reduction. The reduction is complete when the uptake of hydrogen ceases, which is the case after 5 hours.
  • the reaction mixture After the end of the reaction, the reaction mixture is heated to 80 ° C. and the palladium-carbon catalyst is filtered off at this temperature. The filtrate is diluted with 600 ml of "solvent naphtha" and the organic phase, which contains the 2,2'-dichlorohydrazobenzene and the o-chloroaniline formed as a by-product, is separated from the aqueous phase.
  • the o-chloroaniline is dissolved out in a customary manner by washing twice with 5% hydrochloric acid and the “solvent naphtha” is removed in vacuo.
  • the filtered-off palladium-on-carbon catalyst is used at least ten times without purification and the reduction is carried out in the same way. In all subsequent batches, the same yield of 2,2'-dichlorohydrazobenzene as in the starting batch is obtained without reducing the quality.
  • the reduction time is constantly around 5 hours.
  • the chlorine elimination is determined in the aqueous phase by potentiometric titration and is max. 4%, based on o-nitrochlorobenzene.
  • Example 1 is repeated, but 5 g of 2,3-dichloronaphthoquinone- (1,4) is used instead of the hydroxyanthraquinone.
  • the reaction stops at a reaction temperature of 60 ° C and can now be completed by increasing the reaction temperature to 80 ° C.
  • the yield is 80% of theory, based on o-nitrochlorobenzene. The reduction takes 6.25 hours.
  • the yield is 83% of theory of 2,2'-dichlorohydrazobenzene, based on o-nitrochlorobenzene, with a melting point of 84 to 86 ° C, the reaction time is 5 hours. After recycling the platinum catalyst ten times, the yields and the reaction times are constant. The release of chlorine is max. 1.7% of theory, based on o-nitrochlorobenzene.
  • Example 2 The procedure is as in Example 1, but instead of the palladium catalyst 0.25 g of platinum, in the form of 10 g of sulfited 5% platinum-on-carbon catalyst with 50% water content (corresponding to DE-PS 2.105.780) .
  • the yield is 83 96 th. of 2,2-dichlorohydrazobenzene, based on o-nitrochlorobenzene, with a melting point of 85 to 86 ° C, the reaction time is 5 hours. After recycling the platinum catalyst ten times, the yields and the reaction times were constant.
  • the release of chlorine is max. 0.7% of theory, based on o-nitrochlorobenzene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (6)

1. Procédé de préparation du dichloro-2,2' hydrazobenzène par réduction catalytique de l'o-nitro-chlor-benzène au moyen d'hydrogène, dans une lessive alcaline aqueuse et avec addition d'un solvant aromatique non miscible à l'eau, à température élevée et sous pression élevée, en présence d'un catalyseur à base d'un métal noble, procédé caractérisé en ce qu'on utilise, comme co-catalyseur, un dérivé de l'anthraquinone.
2. Procédé selon la revendication 1, caractérisé en ce que le catalyseur à base d'un métal noble est un catalyseur constitué de platine sur charbon, un catalyseur constitué de palladium sur charbon ou un catalyseur constitué de platine sur charbon sulfité.
3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que le dérivé de l'anthraquinone est une hydroxy-anthraquinone.
4. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que le dérivé de l'anthraquinone est la ß-hydroxy-anthraquinone ou la dihydrox-2,6 anthraquinone.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le rapport pondéral de l'o-nitro-chloro-benzène au métal noble est d'environ 4000 à 1500: 1.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le rapport pondéral de l'o-nitro-chloro--benzène au dérivé de l'anthraquinone est d'environ 1 : 0,003 à 1 : 0,008.
EP78100394A 1977-07-27 1978-07-14 Procédé de préparation du dichloro-2,2'-hydrazobenzène Expired EP0000519B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2733747A DE2733747C2 (de) 1977-07-27 1977-07-27 Verfahren zur Herstellung von 2,2 Dichlorhydrazobenzol
DE2733747 1977-07-27

Publications (2)

Publication Number Publication Date
EP0000519A1 EP0000519A1 (fr) 1979-02-07
EP0000519B1 true EP0000519B1 (fr) 1980-07-23

Family

ID=6014887

Family Applications (1)

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EP78100394A Expired EP0000519B1 (fr) 1977-07-27 1978-07-14 Procédé de préparation du dichloro-2,2'-hydrazobenzène

Country Status (6)

Country Link
US (1) US4217307A (fr)
EP (1) EP0000519B1 (fr)
JP (1) JPS5424838A (fr)
CA (1) CA1111449A (fr)
DE (2) DE2733747C2 (fr)
IT (1) IT1097303B (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2833605A1 (de) * 1978-07-31 1980-02-14 Dynamit Nobel Ag Verfahren zur herstellung von hydrazobenzolen durch katalytische hydrierung von nitrobenzolen
US4375559A (en) * 1982-07-15 1983-03-01 Air Products And Chemicals, Inc. Process for the production of hydrazoaromatics using a multi-phase system
US5808154A (en) * 1989-04-05 1998-09-15 Toyo Ink Manufacturing Co., Ltd. Process for the production of an aromatic hydrazo compound
JPH0699380B2 (ja) * 1989-04-05 1994-12-07 東洋インキ製造株式会社 芳香族ヒドラゾ化合物の製造法
US20050037063A1 (en) * 2003-07-21 2005-02-17 Bolton Anthony E. Combined therapies
CA2590533C (fr) * 2004-11-23 2010-09-07 Warner-Lambert Company Llc Derives d'acide 7-(2h-pyrazol-3-yl)-3, 5-dihyroxy-heptanoique comme inhibiteurs de hmg co-a reductase pour le traitement de l'hyperlipidemie
JP2006265129A (ja) * 2005-03-23 2006-10-05 Air Water Inc ３，３’−ビス（トリフルオロメチル）ヒドラゾベンゼンの製造方法
GT200600381A (es) 2005-08-25 2007-03-28 Compuestos organicos
US7741317B2 (en) 2005-10-21 2010-06-22 Bristol-Myers Squibb Company LXR modulators
US7888376B2 (en) 2005-11-23 2011-02-15 Bristol-Myers Squibb Company Heterocyclic CETP inhibitors
US8383660B2 (en) 2006-03-10 2013-02-26 Pfizer Inc. Dibenzyl amine compounds and derivatives
US7919506B2 (en) 2006-03-10 2011-04-05 Pfizer Inc. Dibenzyl amine compounds and derivatives
ES2382009T3 (es) 2006-12-01 2012-06-04 Bristol-Myers Squibb Company Derivados de N-((3-bencil)-2,2-(bis-fenil-)-propan-1-amina como inhibidores de CETP para el tratamiento de aterosclerosis y enfermedades cardiovasculares
CN105143203A (zh) 2013-04-17 2015-12-09 辉瑞大药厂 用于治疗心血管疾病的n-哌啶-3-基苯甲酰胺衍生物
WO2016055901A1 (fr) 2014-10-08 2016-04-14 Pfizer Inc. Composés d'amide substitué
WO2020150473A2 (fr) 2019-01-18 2020-07-23 Dogma Therapeutics, Inc. Inhibiteurs de pcsk9 et leurs procédés d'utilisation
CN111116407B (zh) * 2019-12-16 2022-02-22 浙江秦燕科技股份有限公司 连续催化加氢还原制备dcb还原物的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2794046A (en) * 1954-08-06 1957-05-28 Allied Chem & Dye Corp Method of reducing aromatic nitrogen compounds
US3156724A (en) * 1962-10-25 1964-11-10 Sterling Drug Inc Preparation of 2, 2'-dichlorohydrazobenzene
NL131211C (fr) * 1965-04-05

Also Published As

Publication number Publication date
CA1111449A (fr) 1981-10-27
US4217307A (en) 1980-08-12
IT1097303B (it) 1985-08-31
DE2733747B1 (de) 1979-02-08
JPS5424838A (en) 1979-02-24
DE2860060D1 (en) 1980-11-13
EP0000519A1 (fr) 1979-02-07
JPS627908B2 (fr) 1987-02-19
DE2733747C2 (de) 1979-09-27
IT7826090A0 (it) 1978-07-25

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