WO1994019333A1 - Process for the preparation of bis(2-benzoxazolyl)stilbenes - Google Patents

Process for the preparation of bis(2-benzoxazolyl)stilbenes Download PDF

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Publication number
WO1994019333A1
WO1994019333A1 PCT/US1994/001928 US9401928W WO9419333A1 WO 1994019333 A1 WO1994019333 A1 WO 1994019333A1 US 9401928 W US9401928 W US 9401928W WO 9419333 A1 WO9419333 A1 WO 9419333A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
compounds
carbon atoms
preparation
benzoxazolyl
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.)
Ceased
Application number
PCT/US1994/001928
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English (en)
French (fr)
Inventor
Richard Hsu-Shien Wang
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.)
Eastman Chemical Co
Original Assignee
Eastman Chemical Co
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 Eastman Chemical Co filed Critical Eastman Chemical Co
Priority to KR1019950703454A priority Critical patent/KR960701027A/ko
Priority to JP6519242A priority patent/JPH08507074A/ja
Priority to EP94910157A priority patent/EP0684946B1/en
Priority to DE69402832T priority patent/DE69402832T2/de
Publication of WO1994019333A1 publication Critical patent/WO1994019333A1/en
Anticipated expiration legal-status Critical
Priority to GR970401208T priority patent/GR3023557T3/el
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D263/57—Aryl or substituted aryl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
    • C07D263/64—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings linked in positions 2 and 2' by chains containing six-membered aromatic rings or ring systems containing such rings

Definitions

  • This invention pertains to the preparation of 4,4'-bis(2-benzoxazolyl)stilbene compounds by the reaction of 4,4'—stilbenedicarboxylic acid with 2—aminophenol compounds in the presence of a tin or titanium catalyst and certain solvents.
  • Unsubstituted and substituted 4,4'—bis(2—benz- oxazolyl)stilbene compounds are known compositions of matter which are useful as optical brightening or whitening agents in various polymeric materials, particularly fiber—forming, synthetic polymers.
  • U.S. Patent 4,921,964 discloses the preparation of bis(2—benzoxazolyl)stilbene compounds by the reaction of dialkyl stilbenedicarboxylate ester with various 2—aminophenol compounds in the presence of certain solvents and catalysts.
  • Patent 3,412,089 teaches that the use of 4,4'—stilbenedicarboxylic acid in preparing 4,4'-bis(2—benzoxazolyl)stilbene compounds generally does not give satisfactory results because of the high melting point of the diacid and its limited solubility in many solvents.
  • the '089 patent discloses that 4,4'—stilbenedicarboxylic acid may be used in the preparation of 4,4'—bis(2—benzoxazolyl)stilbene compounds by the reaction thereof with certain 2-amino— phenols using a substantial amount of powerful phosphoric acid dehydrating agents such as pyro— phosphoric and polyphosphoric acids as the reaction medium.
  • 4,4'-bis(2-benzoxazolyl)- stilbene compounds may be obtained in good purity and yields by a simple, one—step process wherein 4,4'—stil ⁇ benedicarboxylic acid is reacted with 2—aminophenol compounds in the presence of a tin or titanium catalyst and certain solvents.
  • the present invention therefore provides a process for the preparation of 4,4'—bis(2- benzoxazolyl)stilbene compounds having the formula
  • each R 1 is independently selected from hydrogen, alkyl of up to 12 carbon atoms and alkoxy of up to 12 carbon atoms.
  • R 1 preferably represents hydrogen or alkyl of up to 4 carbon atoms, especially methyl.
  • the 4,4'—bis(2—benzoxazolyl)stilbene products may be isolated by filtration in a purity which is sufficient for use without further purification.
  • inert, organic solvents examples include naphthalene; alkyl—substituted naphthalene compounds such as methylnaphthalene and di ethylnaphthalene ⁇ ; halogenated naphthalenes such as chloronaphthalene; biphenyl; aromatic ethers such as diphenylether; aromatic alkanes such a ⁇ diphenylethane; and the like.
  • Alkyl—substituted naphthalenes containing 5 a total of 11 to 20 carbon atoms represent the preferred solvents.
  • the amount of solvent employed is not important. However, the weight ratio of the solvent to the total weight of the 4,4'-stilbenedicarboxylic acid with 2—aminophenol reactants typically will be in the
  • the process typically is carried out over a temperature range of 200 to 300°C, preferably 220 to 260°C. Pressure normally is not an important process condition and the process therefore normally is
  • organo—tin and organo—titanium catalyst compounds useful in my novel process are well known
  • the prepared organo—titanium compounds are titanium alkoxides containing a total of up 20 carbon atoms.
  • Titanium tetraisopropoxide and acetyltitanium triiso— propoxide are specific examples of suitable organo— titanium catalysts.
  • the organo tin compounds may be selected from dihydrocarbyltin oxides such as dibutyltin oxide. The amount of the organo—titanium and organo—tin
  • Example 1 The procedure of Example 1 was repeated using equimolar amounts of 2—a ino—4—methylphenol and 2—amino— 4—tertiary butylphenol to obtain 4,4'-bis(5-methyl—2— benzoxazolyl)stilbene and 4,4'—bis(5—t—butyl—2—benzox— azolyl)stilbene in yields of 90 to 95%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/US1994/001928 1993-02-22 1994-02-14 Process for the preparation of bis(2-benzoxazolyl)stilbenes Ceased WO1994019333A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1019950703454A KR960701027A (ko) 1993-02-22 1994-02-14 비스(2-벤족사졸릴)스틸벤의 제조 방법(process for the preparation of bis(2-benzoxazolyl) stilbenes)
JP6519242A JPH08507074A (ja) 1993-02-22 1994-02-14 ビス（２−ベンゾオキサゾリル）スチルベンの製造方法
EP94910157A EP0684946B1 (en) 1993-02-22 1994-02-14 Process for the preparation of bis(2-benzoxazolyl)stilbenes
DE69402832T DE69402832T2 (de) 1993-02-22 1994-02-14 Verfahren zur herstellung von bis(2-benzoxazolyl)stilbenen
GR970401208T GR3023557T3 (en) 1993-02-22 1997-05-26 Process for the preparation of bis(2-benzoxazolyl)stilbenes.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/020,914 US5332828A (en) 1993-02-22 1993-02-22 Process for the preparation of bis (2-benzoxazolyl) stilbenes
US08/020,914 1993-02-22

Publications (1)

Publication Number Publication Date
WO1994019333A1 true WO1994019333A1 (en) 1994-09-01

Family

ID=21801261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/001928 Ceased WO1994019333A1 (en) 1993-02-22 1994-02-14 Process for the preparation of bis(2-benzoxazolyl)stilbenes

Country Status (11)

Country Link
US (1) US5332828A (enExample)
EP (1) EP0684946B1 (enExample)
JP (1) JPH08507074A (enExample)
KR (1) KR960701027A (enExample)
AT (1) ATE152105T1 (enExample)
CA (1) CA2153796A1 (enExample)
DE (1) DE69402832T2 (enExample)
DK (1) DK0684946T3 (enExample)
ES (1) ES2102847T3 (enExample)
GR (1) GR3023557T3 (enExample)
WO (1) WO1994019333A1 (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001064658A1 (en) * 2000-03-02 2001-09-07 Eastman Chemical Company Preparation of mixtures of benzoxazolyl-stilbene compounds

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6565987B2 (en) 1999-11-12 2003-05-20 Eastman Chemical Company Non-exuding optically brightened polyolefin blends
RU2293084C2 (ru) * 2000-10-18 2007-02-10 Циба Спешиалти Кемикэлз Холдинг Инк. Способ получения бис-бензазолиловых соединений
CN102070551B (zh) * 2010-12-29 2012-06-20 河北星宇化工有限公司 2,2’-(4,4’-二苯乙烯基)双苯并噁唑的制备方法
EP4457291A4 (en) * 2021-12-28 2025-10-22 Akdeniz Chemson Kimya Sanayi Ve Ticaret Anonim Sirketi PROCESS FOR THE SYNTHESIS OF BENZOXAZOLE-BASED OPTICAL BRIGHTENERS

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1411999A (fr) * 1964-09-18 1965-09-24 Sumitomo Chemical Co Procédé de fabrication d'agents de blanchiment optiques
DE1939072A1 (de) * 1968-08-01 1970-02-05 Eastman Kodak Co Verfahren zur Herstellung substituierter Benzoxazole
US4921964A (en) * 1989-03-01 1990-05-01 Eastman Kodak Company Process for the preparation of stilbene derivatives

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3412089A (en) * 1963-09-18 1968-11-19 Sumitomo Chemical Co Manufacture of 4, 4'-dibenzoxazol-2-yl stilbene
US3366575A (en) * 1964-03-13 1968-01-30 Nippon Kayaku Kk Enhancement of optical brightening effects by using two or more species of brightening agent
US3586673A (en) * 1968-02-05 1971-06-22 Eastman Kodak Co Preparation of symmetrically and unsymmetrically substituted stilbenebisbenzoxazoles
US3768042A (en) * 1972-06-07 1973-10-23 Motorola Inc Dielectric cavity stripline coupler
DE2526230A1 (de) * 1975-06-12 1976-12-16 Hoechst Ag Neue benzoxazol-derivate, verfahren zu ihrer herstellung und ihre anwendung als optische aufheller
US4291964A (en) * 1980-01-28 1981-09-29 Polaroid Corporation Strobe switch with camera control feature
US4282355A (en) * 1980-02-14 1981-08-04 Hoechst Aktiengesellschaft Process for the manufacture of bis-benzoxazolyl-stilbene compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1411999A (fr) * 1964-09-18 1965-09-24 Sumitomo Chemical Co Procédé de fabrication d'agents de blanchiment optiques
DE1939072A1 (de) * 1968-08-01 1970-02-05 Eastman Kodak Co Verfahren zur Herstellung substituierter Benzoxazole
US4921964A (en) * 1989-03-01 1990-05-01 Eastman Kodak Company Process for the preparation of stilbene derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001064658A1 (en) * 2000-03-02 2001-09-07 Eastman Chemical Company Preparation of mixtures of benzoxazolyl-stilbene compounds

Also Published As

Publication number Publication date
JPH08507074A (ja) 1996-07-30
EP0684946A1 (en) 1995-12-06
DK0684946T3 (enExample) 1997-05-26
DE69402832T2 (de) 1997-07-31
KR960701027A (ko) 1996-02-24
US5332828A (en) 1994-07-26
ATE152105T1 (de) 1997-05-15
CA2153796A1 (en) 1994-09-01
ES2102847T3 (es) 1997-08-01
EP0684946B1 (en) 1997-04-23
DE69402832D1 (de) 1997-05-28
GR3023557T3 (en) 1997-08-29

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