WO1989000556A1 - Preparation de bis-benzenediols amines - Google Patents

Preparation de bis-benzenediols amines Download PDF

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Publication number
WO1989000556A1
WO1989000556A1 PCT/US1988/002309 US8802309W WO8900556A1 WO 1989000556 A1 WO1989000556 A1 WO 1989000556A1 US 8802309 W US8802309 W US 8802309W WO 8900556 A1 WO8900556 A1 WO 8900556A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
amine
benzoquinone
catalyst
benzenediol
Prior art date
Application number
PCT/US1988/002309
Other languages
English (en)
Inventor
Muthiah N. Inbasekaran
Original Assignee
The Dow Chemical Company
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 The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to KR1019890700425A priority Critical patent/KR910004358B1/ko
Priority to AU23003/88A priority patent/AU605634B2/en
Publication of WO1989000556A1 publication Critical patent/WO1989000556A1/fr
Priority to DK105089A priority patent/DK105089A/da
Priority to FI891097A priority patent/FI891097A/fi
Priority to NO89890992A priority patent/NO890992L/no

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C07C215/80—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring containing at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton

Definitions

  • This invention relates to the hydrogenation of benzoquinone compounds. More specifically, it pertains to a process for the hydrogenation of bis (amine-con- taining) dihalobenzoquinone to produce bis (amine-con- taining) benzenediol.
  • Bis (amine-containing) benzenediols are useful as monomers in the preparation of polybenzoxazoles (PBO).
  • Polybenzoxazoles can be prepared by reacting amine-containing benzenediols with bisacids, bisacid halides, bisesters or bisnitriles.
  • Polybenzoxazole fibers have high tensile strength and thermal stability and are desirable for military, aerospace and other applications requiring rigid materials.
  • the known methods for preparing the benzenediol monomers typically involve a multi-step synthesis wherein " expensive reagents are required and overall yield is poor.
  • one method involves ⁇ xi- dative bishydroxylation of hydroquinone with hydrogen peroxide and an alkali to produce 2,5-dihydroxy-p-ben- zoquinone.
  • the present invention is such a straightforward and inexpensive one-step process that provides a high yield of bis (amine-containing) benzenediols.
  • This process comprises contacting bis (amine-containing) dihalobenzoquinones with a molar excess of a reducing agent selected from the group consisting of formic acid, a formate salt and mixtures thereof in the presence of a noble metal-containing catalyst under reaction conditions such that the corresponding bis (amine-containing) benzenediol is produced.
  • amine-containing refers to compounds having -NH2, -NHR, or - 2 substituents wherein R is independently in each occurrence hydrogen, C-*_-J Q alkyl, -3-
  • the bis (amine-containing) benzenediols so pro ⁇ quizzed can be condensed with bisacids, bisacid halides, bisesters or bisnitriles to produce polybenzoxazoles.
  • Polybenzoxazole fibers, as indicated above, are highly useful in various industrial applications.
  • the benzoquinone starting material is contacted with formic acid, a formate salt or a mixture thereof in the presence of a solvent and a catalyst.
  • the pre ⁇ ferred benzoquinone compounds used as the starting material in the present invention correspond to the following general formula:
  • B is 1 , -benzoquinone; each X is independently chlorine, bromine, fluorine or iodine; and R' and R 2 are independently hydrogen, C•-_- ]Q alkyl, arylalkyl or alkylaryl. It is preferred that X is chlorine and that R' and R 2 are each hydrogen.
  • Typical benzoquinone compounds include 2,5- -dichloro-3 > 6-diamino-1 ,4-benzoquinone; 2,5-dibromo- -3,6-diamino-1 ,4-benzoquinone; 2,5-dichloro-3-.6- -bis(benzylamino)-1 ,4-benzoquinone; 2,5-dichloro-3,6- -bis(methylamino)-1 , -benzoquinone; 2,5-dichloro-3 > 6- -bis(dimethylamino)-1 ,4-benzoquinone; 2,5-dichloro-3 > 6- -bis(ethylamino)-!,4-benzoquinone; with 2,5-dichloro- -3 > 6-diamino-1,4-benzoquinone; 2,5-dichloro-3,6-bis- (methylamino)-!
  • benzoquinone starting material 2,5-dichloro-3 » 6-diamino-1,4-benzoquinone.
  • ben ⁇ zoquinone starting materials can be prepared by methods well-known in the art. The typical preparation usually involves the reaction of excess ammonia or ammonium hy ⁇ droxide with tetrahaloquinone. See, e.g., U.S. Patent 4,337,196.
  • the catalyst can be any material which contains a noble metal and will catalyze the conversion of the benzoquinone starting material in the presence of formic acid, a formate salt 0 or a mixture thereof to the desired benzenediol.
  • the catalyst may be unsupported or may be supported on sup ⁇ ports well known in the art such as, for example, alu ⁇ mina, silica, zeolites, titania, alkaline earth metal r carbonates or carbon.
  • Examples of catalysts useful in the practice of the process of this invention include noble metals on carbon, noble metal oxides, and noble metals supported on alkaline earth carbonates.
  • noble metals refers to gold, sil- 0 ver, platinum, palladium, iridium, rhodium, mercury, ruthenium and osmium.
  • Preferred catalysts include pal ⁇ ladium on carbon, platinum on carbon, and platinum . oxide. The most preferred catalyst is palladium on carbon.
  • the catalyst is employed in an amount which is i sufficient to catalyze the conversion of starting ma ⁇ terial in the presence of formic acid, formate salts or mixtures thereof to the corresponding benzenediol.
  • from 0.005 to 0.1 molar equivalents of catalyst are present per equivalent of benzoquinone starting material. More preferably, from 0.02 to 0.06 equivalents of catalyst are present throughout the reaction. It is preferred to add the catalyst to the reaction mixture under an inert atmosphere. Examples of inert atmospheres include argon, helium and nitrogen with nitrogen being preferred.
  • a solvent . is advantageously employed in the process of the present invention.
  • Solvents employed in ' the process of the present invention are polar sol ⁇ vents in which the benezenediol products are soluble.
  • Preferred solvents include water and low molecular weight organic polar compounds.
  • Specific examples of preferred solvents include water, methanol, ethanol, propanol, dimethylformamide and dioxane. Water is the most preferred solvent.
  • Formic acid formate salts or mixtures thereof are used in the process of the present invention as hydrogen transfer agents.
  • formic acid it is preferred that it be aqueous formic acid.
  • concentration of the aqueous formic acid is preferably no less than 5 percent on a weight basis and no greater than 90 percent on a weight basis. It is more -6-
  • the concentration of formic acid be 30 percent on a weight basis.
  • Any formate salt which will function as a hydrogen transfer agent to reduce the benzoquinone and remove the halogens therefrom may be used in the prac ⁇ tice of this invention.
  • M is Na, K, Ce, or (R3)gNH and R ⁇ is hydrogen or hydrocarbyl.
  • hydrocarbyl substituents useful in the practice of this invention include C- j _g alicyclic or aliphatic substituents. It is more pre ⁇ ferred that M be (R- ⁇ J- ⁇ NH and that R3 be hydrogen in each instance.
  • the formate salt is preferably in a polar solvent. Representative examples of suitable polar solvents include water, lower alkanols, and ace- tic acid. It is preferred to use acetic acid as a solvent for the formate salt.
  • the hydrogen transfer agent is used in the practice of this invention in an amount sufficient for the reduction of the benzoquinone starting material to the benzenediol product and the removal of the halogen substituents on the benzoquinone starting material. It is preferred to use the reducing agent in a molar excess based on the molar amount of benzoquinone starting material that is used. It is more preferable to use a 4 to 100 molar excess based on the hydroqui ⁇ none. It is most preferable to use a molar excess of from 10 to 25.
  • the reactants may be added in any order or amount which will allow the reaction to proceed. It is preferred to first mix the benzoquinone reactant and the aqueous formic acid, formate salt or mixtures thereof and then to add the catalyst.
  • the process of the present invention can be carried out at any temperature and pressure at which the reaction will proceed.
  • the process is carried out at a temperature between 20°C and 100°C, more preferably between 40°C and 70°C.
  • the process can be carried out at sub- or superatmospheric pressures with atmospheric pressure being preferred for conve ⁇ nience.
  • the reaction may be allowed to proceed for any length of time sufficient to allow the conversion of at least 50 percent of the starting material.
  • a total reaction time of from 10 minutes to 1 hour is preferred and from 10 minutes to 30 minutes is more preferred.
  • a very small amount of an additional reducing agent such as stannous chloride is added to the reac ⁇ tion mixture to prevent oxidation of the product.
  • the product can be recovered using known recovery methods such as filtration.
  • the product is generally isolated and stored as a hydrohalide salt in order to prevent oxidative decomposition. It is common practice to iso ⁇ late the product as a salt of any mineral acid such as hydrochloric, sulfuric, nitric or phosphoric acid. -8-
  • the conversion of the benzoquinone starting material is at least 70 percent, preferably at least 80 percent and more preferably at least 95 percent.
  • the selectivity to the desired benzenediol is also at least 70 percent, preferably at least 80 percent and more preferably at least 95 percent.
  • the overall yield is at least 50 percent, preferably at least 75 percent and more preferably at least 90 percent.
  • the process can be conducted in a batch or continuous mode.
  • the halogen atoms are removed from the ben ⁇ zoquinone ring system and the benzoquinone is converted to the corresponding benzenediol in a single step.
  • the byproducts of the process are carbon dioxide and/or ammonia.
  • Typical ben ⁇ zenediols include 2,5-diamino-1 ,4-benzenediol, 2,5- -bis(benzylamino)-1 ,4-benzenediol, 2,5-bis(meth l- -amino)-1 ,4-benzenediol, 2,5-bis(ethylamino)-1 ,4- -benzenediol, with 2,5-diamino-1,4-benzenediol, 2,5- -bis(methylamino)-1 ,4-benzenediol and 2,5-bis(benzyl- amino)-1 ,4-benzenediol being preferred.
  • the most preferred benzenediol is 2,5-diamino-1 ,4-benzenediol.
  • a 400-mg portion of a 10 percent palladium-on- -carbon catalyst was added to a reaction vessel containing a vigorously stirred suspension of 4.14 g (20 mmole) of 2,5-dichloro-3,6-diamino-1 ,4-benzoquinone in 30 ml of water and 20 ml of 88 percent formic acid under a nitrogen atmosphere. The nitrogen was removed and mixture was stirred and heated to 60°C during a 15-minute period. The mixture was kept at 60°C for 10 minutes. About 50 mg of stannous chloride was added and the mixture was filtered and washed with 15 ml of water. Hydrogen chloride gas was passed into the fil ⁇ trate to saturation.
  • a 400-mg portion of a 10 percent palladium-on- -carbon catalyst was added to a reaction vessel containing a vigorously stirred suspension of 1.40 g (7 mmol) of 2,5-dichloro-3»6-diamlno-1 ,4-benzoquinone, 3-15 g (50 mmol) of ammonium formate, 20 ml of water and 5 ml of acetic acid under a nitrogen atmosphere. The nitrogen was removed and the mixture was stirred at ambient temperature for one hour. The mixture was then heated and stirred at 60°C-80°C for 2 hours. About 50 mg of stannous chloride and 10 ml of HC1 was added and the catalyst was filtered off.

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

Abstract

Des bis-benzenediols aminés sont préparés par hydrogénation et déshalogénation de bis-dihalobenzoquinones aminés en utilisant de l'acide formique, des sels de formate ou des mélanges de ceux-ci en présence d'un catalyseur en métal noble. Un exemple d'un composé produit par ce procédé est le 2,5-diamino-1,4-benzenediol. Les benzènes diols produits par le procédé de cette invention sont utiles en tant que monomères dans la préparation de polybenzoxazoles ayant une grande stabilité thermique et une résistance à la compression élevées.
PCT/US1988/002309 1987-07-09 1988-07-08 Preparation de bis-benzenediols amines WO1989000556A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1019890700425A KR910004358B1 (ko) 1987-07-09 1988-07-08 비스(아민-함유)벤젠디올의 제조방법
AU23003/88A AU605634B2 (en) 1987-07-09 1988-07-08 Preparation of bis (amine-containing) benzenediols
DK105089A DK105089A (da) 1987-07-09 1989-03-03 Fremstilling af bis(amin-holdige)benzendioler
FI891097A FI891097A (fi) 1987-07-09 1989-03-08 Framstaellning av bis-amingrupp innehaollande bensendioler.
NO89890992A NO890992L (no) 1987-07-09 1989-03-08 Fremstilling av bis(amin-holdige) benzendioler.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7124187A 1987-07-09 1987-07-09
US071,241 1987-07-09

Publications (1)

Publication Number Publication Date
WO1989000556A1 true WO1989000556A1 (fr) 1989-01-26

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/002309 WO1989000556A1 (fr) 1987-07-09 1988-07-08 Preparation de bis-benzenediols amines

Country Status (6)

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EP (1) EP0324847A4 (fr)
JP (1) JPH02500108A (fr)
KR (1) KR910004358B1 (fr)
DK (1) DK105089A (fr)
FI (1) FI891097A (fr)
WO (1) WO1989000556A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR880100684A (el) * 1988-10-11 1990-11-29 Dow Chemical Co Μεθοδος παρασκευης δις(περιεχουσων αμινομαδα)βενζολοδιολων.
US6313132B1 (en) 1997-03-27 2001-11-06 Pharmacia Ab Therapeutically active diarylpropylamines; their pharmaceutically acceptable salts; a method for their preparation and method for their use
US11472923B2 (en) * 2019-03-25 2022-10-18 Brown University Nanoparticle catalyst for synthesizing polybenzoxazole with controlled polymerization

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337196A (en) * 1980-08-29 1982-06-29 United States Of America Method for producing 3,6-bis(carboethoxyamino)-2,5-diaziridinyl-1,4-benzoquinone
US4581349A (en) * 1984-06-21 1986-04-08 University Of Maryland Certain benzodiimidazoles and their use as radiation sensitizers
US4692554A (en) * 1983-10-18 1987-09-08 Mitsui Toatsu Chemicals, Inc. Process for producing 1,3-bis(3-aminophenoxy)benzene
WO1987006930A1 (fr) * 1986-05-16 1987-11-19 The Dow Chemical Company Preparation de diamino- et dialkylaminobenzenediols

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337196A (en) * 1980-08-29 1982-06-29 United States Of America Method for producing 3,6-bis(carboethoxyamino)-2,5-diaziridinyl-1,4-benzoquinone
US4692554A (en) * 1983-10-18 1987-09-08 Mitsui Toatsu Chemicals, Inc. Process for producing 1,3-bis(3-aminophenoxy)benzene
US4581349A (en) * 1984-06-21 1986-04-08 University Of Maryland Certain benzodiimidazoles and their use as radiation sensitizers
WO1987006930A1 (fr) * 1986-05-16 1987-11-19 The Dow Chemical Company Preparation de diamino- et dialkylaminobenzenediols

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 96, No. 13, issued 29 March 1982 (Columbus, Ohio. USA), M. PARDO et al, "Synthesis and Structure of Phenylazo-Hydroquinones", see page 663, cols. 1 and 2 of Abstract No. 103770n- Liebigs Ann. Chem. 1982 (1), pp. 99-111 (Ger.) *
Helvetica Chimica Acta Volume 39, No. 38, pp. 335-340 (1956), A. MARXER, "38. Uber 2,5-Bis-Athylenimino-Hydrochinon", see page 337 at 3,6-Dichlor-2,5-Diamino-Hydrochinon (XIII). *
Journal of the American Chemical Society, Volume 68, pp. 261-265 (1946), R. BALTZLY et al, "The Catalytic Hydrogenolysis of Halogen Compounds". *
See also references of EP0324847A4 *
The Merck Index, Tenth Edition. 1983 (N.J.), page 605 "Formic Acid". *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR880100684A (el) * 1988-10-11 1990-11-29 Dow Chemical Co Μεθοδος παρασκευης δις(περιεχουσων αμινομαδα)βενζολοδιολων.
US6313132B1 (en) 1997-03-27 2001-11-06 Pharmacia Ab Therapeutically active diarylpropylamines; their pharmaceutically acceptable salts; a method for their preparation and method for their use
US11472923B2 (en) * 2019-03-25 2022-10-18 Brown University Nanoparticle catalyst for synthesizing polybenzoxazole with controlled polymerization

Also Published As

Publication number Publication date
JPH02500108A (ja) 1990-01-18
EP0324847A4 (en) 1991-03-20
DK105089D0 (da) 1989-03-03
KR890701541A (ko) 1989-12-20
KR910004358B1 (ko) 1991-06-26
FI891097A0 (fi) 1989-03-08
DK105089A (da) 1989-03-03
FI891097A (fi) 1989-03-08
EP0324847A1 (fr) 1989-07-26

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