JPH04221328A - Production of iodinated 9,9-dialkylfluorene - Google Patents
Production of iodinated 9,9-dialkylfluoreneInfo
- Publication number
- JPH04221328A JPH04221328A JP40543590A JP40543590A JPH04221328A JP H04221328 A JPH04221328 A JP H04221328A JP 40543590 A JP40543590 A JP 40543590A JP 40543590 A JP40543590 A JP 40543590A JP H04221328 A JPH04221328 A JP H04221328A
- Authority
- JP
- Japan
- Prior art keywords
- dialkylfluorene
- iodine chloride
- reaction
- iodine
- mono
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000035484 reaction time Effects 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 239000012442 inert solvent Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012336 iodinating agent Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- NMEQHHYHRUXYEN-UHFFFAOYSA-N 1,2-diiodo-9h-fluorene Chemical class C1=CC=C2CC3=C(I)C(I)=CC=C3C2=C1 NMEQHHYHRUXYEN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- BEFAQJJPFPNXIG-UHFFFAOYSA-N 1-nitro-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C([N+](=O)[O-])=CC=C2 BEFAQJJPFPNXIG-UHFFFAOYSA-N 0.000 description 1
- GYOWFFGLGGCYSQ-UHFFFAOYSA-N 2,7-diiodo-9,9-dimethylfluorene Chemical compound C1=C(I)C=C2C(C)(C)C3=CC(I)=CC=C3C2=C1 GYOWFFGLGGCYSQ-UHFFFAOYSA-N 0.000 description 1
- DVLSJPCXPNKPRJ-UHFFFAOYSA-N 2-iodo-9,9-dimethylfluorene Chemical compound C1=C(I)C=C2C(C)(C)C3=CC=CC=C3C2=C1 DVLSJPCXPNKPRJ-UHFFFAOYSA-N 0.000 description 1
- LMPAOSZGWWFJBA-UHFFFAOYSA-N 9,9-diethyl-2-iodofluorene Chemical compound C1=C(I)C=C2C(CC)(CC)C3=CC=CC=C3C2=C1 LMPAOSZGWWFJBA-UHFFFAOYSA-N 0.000 description 1
- DXLHOCYBTWOELM-UHFFFAOYSA-N 9,9-diethylfluorene Chemical compound C1=CC=C2C(CC)(CC)C3=CC=CC=C3C2=C1 DXLHOCYBTWOELM-UHFFFAOYSA-N 0.000 description 1
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LFGVUBNSHXWLSE-UHFFFAOYSA-N ICl.Cl Chemical compound ICl.Cl LFGVUBNSHXWLSE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- -1 iodo compound Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、染料、医薬、高分子モ
ノマーなどの中間体として重要なモノ及びジヨード置換
９，９−ジアルキルフルオレンの新規製造法に関する。FIELD OF THE INVENTION The present invention relates to a new method for producing mono- and diiodo-substituted 9,9-dialkylfluorenes, which are important intermediates for dyes, medicines, polymeric monomers, etc.
【０００２】0002
【従来の技術】フルオレンのハロゲン化には、スルフリ
ルクロライドによる塩素化（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏ
ｃ．，６６．２１２７．１９４４）、Ｎ−ブロモスクシ
イミドによる臭素化（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，
８０．４３２７．１９５８）などがある。 しかしな
がら、中間体としてはヨード体がもっとも反応性に富む
ために、その工業的製法の確立が望まれている。[Prior Art] For halogenation of fluorene, chlorination with sulfuryl chloride (J. Am. Chem. So
c. , 66.2127.1944), bromination with N-bromosuccinimide (J. Am. Chem. Soc.,
80.4327.1958). However, since the iodo compound is the most reactive intermediate, it is desired to establish an industrial method for its production.
【０００３】ベンゼン誘導体の沃素化反応については、
塩化沃素を沃素化剤として用いた反応例が報告されてい
るが、フルオレン誘導体について用いた例は報告されて
いない。塩化沃素は、代表的な沃素化剤である沃素に比
べ取扱いが容易であり、酸化剤を必要としないなどの利
点をもっている。Regarding the iodination reaction of benzene derivatives,
Although reaction examples using iodine chloride as an iodinating agent have been reported, no examples using fluorene derivatives have been reported. Iodine chloride has the advantage that it is easier to handle than iodine, which is a typical iodizing agent, and does not require an oxidizing agent.
【０００４】一方、一般的に沃素を用いる反応において
は、硝酸、過沃素酸などの酸化剤を必要とする。しかし
ながら、過沃素酸は爆発の危険性があり、工業的製法に
用いるには問題を残している。また、硝酸を用いたフル
オレン誘導体の反応では、毒性の高いニトロフルオレン
誘導体が副生成物として生成するため、この反応には不
向きである。On the other hand, reactions using iodine generally require an oxidizing agent such as nitric acid or periodic acid. However, periodic acid has a risk of explosion, and its use in industrial production methods remains problematic. Further, in the reaction of fluorene derivatives using nitric acid, a highly toxic nitrofluorene derivative is produced as a by-product, so this reaction is not suitable.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、塩化
沃素を用い、低コストで操作が容易かつ安全に、しかも
高収率でモノ及びジヨード置換９，９−ジアルキルフル
オレンを製造する方法を提供することである。SUMMARY OF THE INVENTION The object of the present invention is to provide a method for producing mono- and diiodo-substituted 9,9-dialkylfluorenes using iodine chloride at low cost, easy to operate, safe, and in high yield. It is to provide.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、塩化沃素
を本反応に応用すべく鋭意検討した。その結果、塩化沃
素と反応させることをにより、目的の９，９−ジアルキ
ルモノ及びジヨードフルオレンを高収率で製造し得るこ
とを見い出した。[Means for Solving the Problems] The present inventors have made extensive studies to apply iodine chloride to this reaction. As a result, it was found that the desired 9,9-dialkyl mono- and diiodofluorenes could be produced in high yield by reacting with iodine chloride.
【０００７】すなわち、本発明は原料として９，９−ジ
アルキルフルオレンを用い、塩化沃素と反応させること
を特徴とする９，９−ジアルキル−２− ヨードフルオ
レン及び９，９−ジアルキル−２，７−ジヨードフルオ
レンの製造法である。That is, the present invention uses 9,9-dialkylfluorene as a raw material and reacts it with iodine chloride. This is a method for producing diiodofluorene.
【０００８】本発明の方法では、反応に有機溶媒または
酸性の水溶媒を反応溶媒として用いることができる。通
常、不活性溶媒が使用されるが、好ましい溶媒としては
、反応性の観点からアルコール、酢酸、塩酸、硫酸等の
極性プロトン溶媒があげられる。ここで用いる溶媒量は
、原料の９，９−ジアルキルフルオレンの通常２〜２０
重量倍、好ましくは３〜７重量倍である。In the method of the present invention, an organic solvent or an acidic aqueous solvent can be used as a reaction solvent. Usually, an inert solvent is used, and preferred solvents include polar protic solvents such as alcohol, acetic acid, hydrochloric acid, and sulfuric acid from the viewpoint of reactivity. The amount of solvent used here is usually 2 to 20% of the 9,9-dialkylfluorene used as the raw material.
weight, preferably 3 to 7 times the weight.
【０００９】本発明の方法では、沃素化剤として塩化沃
素を用いる。塩化沃素は固体であるが、塩酸水溶液中で
安定であり、その取扱いが安定で、酸化剤を必要としな
いなどの利点をもっている。In the method of the present invention, iodine chloride is used as the iodizing agent. Although iodine chloride is a solid, it is stable in an aqueous hydrochloric acid solution, is stable to handle, and has the advantage of not requiring an oxidizing agent.
【００１０】モノヨード体を製造する場合には、沃素化
剤の使用量は、原料の９，９−ジアルキルフルオレンに
対して通常１．０〜３モル倍、好ましくは１．１〜２．
０モル倍である。When producing a monoiodo compound, the amount of the iodinating agent used is usually 1.0 to 3 moles, preferably 1.1 to 2.
It is 0 mole times.
【００１１】一方、ジヨード体を製造する場合には、沃
素化剤の使用量は、原料の９，９−ジアルキルフルオレ
ンに対して通常２．０〜１０モル倍、好ましくは３．０
〜７．０モル倍である。On the other hand, when producing a diiodo compound, the amount of the iodizing agent used is usually 2.0 to 10 moles, preferably 3.0 times, based on the raw material 9,9-dialkylfluorene.
~7.0 times the mole.
【００１２】モノヨード体を製造する場合には、反応温
度は３０〜８０℃、好ましくは５０〜７５℃である。反
応時間は２〜８時間、好ましくは３〜６時間である。ま
た、ジヨード体を製造する場合には、反応温度は６０〜
９０℃、好ましくは８０〜９０℃である。反応時間は５
〜２０時間、好ましくは１２〜１５時間である。[0012] When producing a monoiodo compound, the reaction temperature is 30 to 80°C, preferably 50 to 75°C. The reaction time is 2 to 8 hours, preferably 3 to 6 hours. In addition, when producing a diiodo compound, the reaction temperature is 60~
The temperature is 90°C, preferably 80-90°C. Reaction time is 5
-20 hours, preferably 12-15 hours.
【００１３】モノ・ジヨード体いずれを製造する場合に
も通常、常圧下で反応を行う。 反応終了後、トルエ
ンで抽出し、有機層をチオ硫酸ナトリウム水溶液で中和
した後、減圧下で溶媒を除去すれば容易に目的物が得ら
れる。[0013] In the production of both mono- and di-iodo compounds, the reaction is usually carried out under normal pressure. After the reaction is completed, the desired product is easily obtained by extracting with toluene, neutralizing the organic layer with an aqueous sodium thiosulfate solution, and removing the solvent under reduced pressure.
【００１４】[0014]
【発明の効果】実施例に見られるように、本発明の方法
によれば、簡便、安全に、かつ低コストで９，９−ジア
ルキルフルオレンの沃素化を行うことができる。更に、
沃素化剤の添加量、反応温度、及び反応時間を調節する
ことで、モノヨード体、ジヨード体を選択的に製造する
ことができる。As seen in the Examples, according to the method of the present invention, 9,9-dialkylfluorene can be iodized simply, safely, and at low cost. Furthermore,
By adjusting the amount of the iodinating agent added, the reaction temperature, and the reaction time, monoiodo compounds and diiodo compounds can be selectively produced.
【００１５】すなわち、本発明は、９，９−ジアルキル
−２− ヨードフルオレン及び９，９−ジアルキル−２
，７− ジヨードフルオレンの、工業的に優れた製造法
を提供するものである。That is, the present invention provides 9,9-dialkyl-2-iodofluorene and 9,9-dialkyl-2-iodofluorene.
, 7-diiodofluorene.
【００１６】[0016]
【実施例】以下、本発明の方法を実施例により説明する
。EXAMPLES The method of the present invention will be explained below using examples.
【００１７】実施例１９，９−ジメチルフルオレン２０
ｇ（０．１０モル）、酢酸８０ｍｌを混合し、７０℃に
昇温した後、５０％塩化沃素塩酸水溶液５０ｇ（０．１
５モル）を加え、５時間反応させた。その後、１００ｍ
ｌのトルエンで抽出し、１０％チオ硫酸ナトリウム水溶
液４０ｍｌで残存沃素を中和し、有機層を濃縮後減圧蒸
留することにより、３１．２ｇの９，９−ジメチル−２
−ヨードフルオレンを得た。Example 19,9-dimethylfluorene 20
g (0.10 mol) and 80 ml of acetic acid were mixed and heated to 70°C, and then 50 g (0.1
5 mol) was added and reacted for 5 hours. Then 100m
31.2 g of 9,9-dimethyl-2
-Iodofluorene was obtained.
【００１８】収率９４．７％、沸点１３６〜１３７℃／
１．５ｍｍＨｇ、純度９９．３％（ガスクロマトグラフ
ィー分析による）Yield 94.7%, boiling point 136-137°C/
1.5mmHg, purity 99.3% (by gas chromatography analysis)
【００１９】元素分析（理論値 ／
実測値）Ｃ ； ５６．１０ ／
５６．２４Ｈ ； ４．３９ ／
４．３５Elemental analysis (theoretical value /
Actual value) C; 56.10 /
56.24H; 4.39/
4.35
【００２０】実施例２９，９−ジ
メチルフルオレン２０ｇ（０．１０モル）、ｎ−ブタノ
ール６０ｍｌを混合し、９０℃に昇温した後、５０％塩
化沃素１６７ｇ（０．５０モル） を加え、１３時間反
応させた。その後、１００ｍｌのトルエンで抽出し、１
０％チオ硫酸ナトリウム水溶液６０ｍｌで残存沃素を中
和し、有機層を濃縮後減圧蒸留することにより、４２．
２ｇの９，９−ジメチル−２，７−ジヨードフルオレン
を得た。Example 29 20 g (0.10 mol) of 9,9-dimethylfluorene and 60 ml of n-butanol were mixed and heated to 90°C, and then 167 g (0.50 mol) of 50% iodine chloride was added. Allowed time to react. Then, extract with 100ml of toluene and
42. The remaining iodine was neutralized with 60 ml of 0% sodium thiosulfate aqueous solution, and the organic layer was concentrated and then distilled under reduced pressure.
2 g of 9,9-dimethyl-2,7-diiodofluorene was obtained.
【００２１】収率９１．９％、沸点１７０〜１７１℃／
１．５ｍｍＨｇ、純度９８．７％（ガスクロマトグラフ
ィー分析による）元素分析（理論値 ／ 実測値）
Ｃ ； ４０．３０ ／ ４０．
１８Ｈ ； ２．９３ ／
２．９８Yield 91.9%, boiling point 170-171°C/
1.5 mmHg, purity 98.7% (by gas chromatography analysis) Elemental analysis (theoretical value / actual value) C; 40.30 / 40.
18H; 2.93/
2.98
【００２２】実施例３９，９−ジエチルフ
ルオレン２２ｇ（０．１０モル）、５％塩酸水８０ｍｌ
を分散させ、７０℃に昇温した後、５０％塩化沃素塩酸
水溶液５０ｇ（０．１５モル） を加え、５時間反応さ
せた。その後、１００ｍｌのトルエンで抽出し、１０％
チオ硫酸ナトリウム水溶液４０ｍｌで残存沃素を中和し
、有機層を濃縮後減圧蒸留することにより、３２．５ｇ
の９，９−ジエチル−２−ヨードフルオレンを得た。Example 3 22 g (0.10 mol) of 9,9-diethylfluorene, 80 ml of 5% hydrochloric acid water
After dispersing the mixture and raising the temperature to 70°C, 50 g (0.15 mol) of a 50% aqueous chloroiodine-hydrochloric acid solution was added, and the mixture was reacted for 5 hours. Then, extract with 100 ml of toluene and extract 10%
The remaining iodine was neutralized with 40 ml of sodium thiosulfate aqueous solution, and the organic layer was concentrated and distilled under reduced pressure to obtain 32.5 g.
9,9-diethyl-2-iodofluorene was obtained.
【００２３】収率９４．３％、沸点１５８〜１５９℃／
１．５ｍｍＨｇ、純度９８．１％（ガスクロマトグラフ
ィー分析による）元素分析（理論値 ／ 実測値）
Ｃ ； ５８．４７ ／ ５８．
４０Ｈ ； ５．２０ ／
５．３８Yield 94.3%, boiling point 158-159°C/
1.5 mmHg, purity 98.1% (by gas chromatography analysis) Elemental analysis (theoretical value / actual value) C; 58.47 / 58.
40H; 5.20/
5.38
【００２４】実施例４〜６同様にして、置
換基を変えた９，９−ジアルキル−２− ヨードフルオ
レン及び９，９−ジアルキル−２，７−ヨードフルオレ
ンを合成し、収率及び純度、元素分析値、沸点を求め、
表１にまとめた。In the same manner as in Examples 4 to 6, 9,9-dialkyl-2-iodofluorene and 9,9-dialkyl-2,7-iodofluorene with different substituents were synthesized, and the yield, purity, and elemental Find the analysis value and boiling point,
The results are summarized in Table 1.
【００２５】[0025]
【表１】[Table 1]
Claims (1)
素と反応させることを特徴とする沃素化９，９−ジアル
キルフルオレンの製造方法。1. A method for producing iodinated 9,9-dialkylfluorene, which comprises reacting 9,9-dialkylfluorene with iodine chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40543590A JP2779366B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing iodinated 9,9-dialkylfluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40543590A JP2779366B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing iodinated 9,9-dialkylfluorene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04221328A true JPH04221328A (en) | 1992-08-11 |
| JP2779366B2 JP2779366B2 (en) | 1998-07-23 |
Family
ID=18515031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40543590A Expired - Lifetime JP2779366B2 (en) | 1990-12-25 | 1990-12-25 | Method for producing iodinated 9,9-dialkylfluorene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2779366B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997020877A2 (en) * | 1995-12-01 | 1997-06-12 | Ciba Specialty Chemicals Holding Inc. | Poly(9,9'-spiro-bisfluorenes), the production and use of same |
| JPH11510535A (en) * | 1995-07-28 | 1999-09-14 | ザ ダウ ケミカル カンパニー | 2,7-Aryl-9-substituted fluorene and 9-substituted fluorene oligomers and polymers |
| US6593450B2 (en) | 1995-07-28 | 2003-07-15 | Dow Global Technologies Inc. | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
-
1990
- 1990-12-25 JP JP40543590A patent/JP2779366B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6380445B1 (en) | 1995-01-12 | 2002-04-30 | Vantico Inc. | Poly(9,9'-spirobisfluorenes), their production and their use |
| US6559277B2 (en) | 1995-01-12 | 2003-05-06 | Vantico Inc. | Poly(9,9′-spirobisfluorenes), their production and their use |
| JPH11510535A (en) * | 1995-07-28 | 1999-09-14 | ザ ダウ ケミカル カンパニー | 2,7-Aryl-9-substituted fluorene and 9-substituted fluorene oligomers and polymers |
| US6512083B1 (en) | 1995-07-28 | 2003-01-28 | Dow Global Technologies Inc. | Fluorene-containing polymers and compounds useful in the preparation thereof |
| US6514632B1 (en) | 1995-07-28 | 2003-02-04 | Dow Global Technologies Inc. | Fluorene-containing polymers and compounds useful in the preparation thereof |
| US6593450B2 (en) | 1995-07-28 | 2003-07-15 | Dow Global Technologies Inc. | 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers |
| US6900285B2 (en) | 1995-07-28 | 2005-05-31 | Dow Global Technologies Inc. | Fluorene-containing polymers and compounds useful in the preparation thereof |
| WO1997020877A2 (en) * | 1995-12-01 | 1997-06-12 | Ciba Specialty Chemicals Holding Inc. | Poly(9,9'-spiro-bisfluorenes), the production and use of same |
| WO1997020877A3 (en) * | 1995-12-01 | 1997-09-12 | Ralf-Roman Rietz | Poly(9,9'-spiro-bisfluorenes), the production and use of same |
| US6132641A (en) * | 1995-12-01 | 2000-10-17 | Vantico, Inc. | Composition and support material comprising poly(9,9'-spiro-bisfluorenes) |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2779366B2 (en) | 1998-07-23 |
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