JPS6245232B2 - - Google Patents
Info
- Publication number
- JPS6245232B2 JPS6245232B2 JP56214417A JP21441781A JPS6245232B2 JP S6245232 B2 JPS6245232 B2 JP S6245232B2 JP 56214417 A JP56214417 A JP 56214417A JP 21441781 A JP21441781 A JP 21441781A JP S6245232 B2 JPS6245232 B2 JP S6245232B2
- Authority
- JP
- Japan
- Prior art keywords
- pentanediol
- trimethyl
- oils
- fluoroacetophenone
- compound
- 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
- 150000001875 compounds Chemical class 0.000 claims description 9
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 claims description 5
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- -1 cyclic acetal Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Description
本発明は以下の構造式で示される２−メチル−
２（4′−フルオロフエニル）−４−イソプロピル
−５・５−ジメチル−１・３−ジオキサンおよび
その製造法に関する。
上記、本発明化合物は、構造式：
で示される新規化合物であり、凝固点が低く、沸
点が高く、広い温度範囲で高い流動性（低粘性）
を保持し得る安定な液状物質であり、高速記録イ
ンキジエツト等の特殊インキ用添加剤、精密機器
の潤滑油、絶縁油、特にコンデンサー油、トラン
ス油、ケーブル油、遮断機油、低温条件で用いる
その他の機能流体用ベースの分野に使用できる。
本発明化合物は２・２・４−トリメチル−１・
３−ペンタンジオールを原料とし、これにｐ−フ
ルオロアセトフエノンを加え、通常用いられるエ
ステル化触媒の存在下に脱水反応させることによ
り容易に得ることができる。
原料となる２・２・４−トリメチル−１・３−
ペンタンジオールは、立体構造的にみて二つの水
酸基が環状アセタールを形成するのに適した位置
にあり、本発明化合物を高収率で得ることがで
き、かつ、この構造上の特徴から生成した還状ア
セタールは特徴的なヒンダード構造を六員環にも
たらすため、安定な化合物が得られるものと考え
られる。
２・２・４−トリメチル−１・３−ペンタンジ
オールとｐ−フルオロアセトフエノンとの脱水反
応は、両者ほぼ当量用い、適当な共沸脱水用の溶
剤、例えばベンゼン等の芳香族溶剤を用いて通常
のエステル化触媒、例えばｐ−トルエンスルホン
酸の存在下に加熱条件で反応させ、生成水を系外
に取り出すことによつて行なうのが好ましい。芳
香族系溶剤を用いて行なうときは還流条件、例え
ばベンゼンの場合は80℃以上で行なうのが好まし
く、反応時間１〜２時間で、約90％以上の収率で
目的化合物を得ることができる。
この脱水反応は、無溶媒でも実施できるが芳香
族溶媒を用いた共沸脱水反応は反応条件が穏和で
コントロールが容易であり、しかも収率が極めて
高いため工業的に生産性に非常に優れている。
本発明化合物の物理的諸特性を表−１に示す。
The present invention relates to 2-methyl-
The present invention relates to 2(4'-fluorophenyl)-4-isopropyl-5,5-dimethyl-1,3-dioxane and a method for producing the same. The above compound of the present invention has the structural formula: It is a new compound with a low freezing point, high boiling point, and high fluidity (low viscosity) over a wide temperature range.
It is a stable liquid substance capable of retaining high-speed recording ink jets and other special inks, lubricating oils for precision equipment, insulating oils, especially condenser oils, transformer oils, cable oils, circuit breaker oils, and other oils used in low-temperature conditions. Can be used in functional fluid based fields. The compound of the present invention is 2,2,4-trimethyl-1.
It can be easily obtained by using 3-pentanediol as a raw material, adding p-fluoroacetophenone thereto, and carrying out a dehydration reaction in the presence of a commonly used esterification catalyst. 2,2,4-trimethyl-1,3- as a raw material
In pentanediol, two hydroxyl groups are located in suitable positions to form a cyclic acetal from a steric structure, and the compound of the present invention can be obtained in high yield. Since acetals have a characteristic hindered structure in the six-membered ring, it is thought that stable compounds can be obtained. In the dehydration reaction of 2,2,4-trimethyl-1,3-pentanediol and p-fluoroacetophenone, approximately equivalent amounts of both are used, and an appropriate solvent for azeotropic dehydration, for example, an aromatic solvent such as benzene, is used. It is preferable to conduct the reaction under heating conditions in the presence of a conventional esterification catalyst, such as p-toluenesulfonic acid, and to remove the produced water from the system. When using an aromatic solvent, it is preferably carried out under reflux conditions, for example at 80°C or higher in the case of benzene, and the target compound can be obtained in a yield of about 90% or more in a reaction time of 1 to 2 hours. . Although this dehydration reaction can be carried out without a solvent, the azeotropic dehydration reaction using an aromatic solvent has mild reaction conditions, is easy to control, and has an extremely high yield, making it extremely industrially productive. There is. Table 1 shows the physical properties of the compound of the present invention.
【表】
以下実施例をあげて本発明を説明する。
実施例 １
２・２・４−トリメチル−１・３−ペンタンジ
オール0.73モル（106.7ｇ）にｐ−フルオロアセ
トフエノン0.74モル（102ｇ）、ｐ−トルエンスル
ホン酸0.5ｇおよびベンゼン200mlをデイーン・ス
タークの蒸溜器を付した撹拌機付きフラスコに仕
込み、生成する水を共沸により系外に除きながら
100℃で２時間撹拌した。生成物に無水炭酸カリ
ウム約30ｇを加え中和し、乾燥後塩を過した
後、ベンゼン層を蒸溜し、0.6mmHgで80〜83℃の
溜分182ｇ（収率93％）を得た。生成物の物理特
性を表−１に示す。
生成物を以下の条件でガスクロマトグラフイー
にかけたところ第３図に示すごとき単一のピーク
を示した。
ガスクロマトグラフイー条件
検出器：FID
カラム（ステンレス製）：長さ１ｍ
充填材SE−30
キヤリヤーガス：窒素ガス 0.8Kg／cm2
インジエクシヨン温度：210℃
展開温度：190℃
チヤート送り速度：20mm／分[Table] The present invention will be explained below with reference to Examples. Example 1 0.73 moles (106.7 g) of 2,2,4-trimethyl-1,3-pentanediol, 0.74 moles (102 g) of p-fluoroacetophenone, 0.5 g of p-toluenesulfonic acid and 200 ml of benzene were added to Dean Stark. The water is poured into a flask with a stirrer equipped with a distiller, and the water produced is removed from the system by azeotropy.
The mixture was stirred at 100°C for 2 hours. Approximately 30 g of anhydrous potassium carbonate was added to the product to neutralize it, and after drying and filtering off the salt, the benzene layer was distilled to obtain 182 g (yield: 93%) of a fraction having a temperature of 80 to 83° C. at 0.6 mmHg. The physical properties of the product are shown in Table-1. When the product was subjected to gas chromatography under the following conditions, it showed a single peak as shown in FIG. Gas chromatography conditions Detector: FID Column (stainless steel): Length 1m Packing material SE-30 Carrier gas: Nitrogen gas 0.8Kg/cm 2 Injection temperature: 210℃ Development temperature: 190℃ Chart feed speed: 20mm/min
第１図は２−メチル−２（4′−フルオルフエニ
ル）−４−イソプロピル−５・５−ジメチル−
１・３−ジオキサンのIRチヤート、第２図は同
NMRチヤート、第３図は同ガスクロマトグラム
を示す。
Figure 1 shows 2-methyl-2(4'-fluorophenyl)-4-isopropyl-5,5-dimethyl-
IR chart of 1,3-dioxane, Figure 2 is the same.
NMR chart, Figure 3 shows the same gas chromatogram.
Claims (1)
ジオールとｐ−フルオロアセトフエノンを反応さ
せることを特徴とする構造式： で示される化合物の製造方法。 ３ ２・２・４−トリメチル−１・３−ペンタン
ジオールとｐ−フルオロアセトフエノンの反応を
有機溶剤の存在下に共沸脱水させる第２項記載の
方法。[Claims] 1 Structural formula: The compound shown in 2 Structural formula characterized by reacting 2,2,4-trimethyl-1,3-pentanediol and p-fluoroacetophenone: A method for producing a compound represented by 3. The method according to item 2, wherein the reaction between 2,2,4-trimethyl-1,3-pentanediol and p-fluoroacetophenone is azeotropically dehydrated in the presence of an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56214417A JPS58116480A (en) | 1981-12-28 | 1981-12-28 | 2-methyl-2(4'-fluorophenyl)-4-isopropyl-5,5-dimethyl-1,3 dioxane and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56214417A JPS58116480A (en) | 1981-12-28 | 1981-12-28 | 2-methyl-2(4'-fluorophenyl)-4-isopropyl-5,5-dimethyl-1,3 dioxane and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58116480A JPS58116480A (en) | 1983-07-11 |
| JPS6245232B2 true JPS6245232B2 (en) | 1987-09-25 |
Family
ID=16655438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56214417A Granted JPS58116480A (en) | 1981-12-28 | 1981-12-28 | 2-methyl-2(4'-fluorophenyl)-4-isopropyl-5,5-dimethyl-1,3 dioxane and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58116480A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100727997B1 (en) | 2005-10-10 | 2007-06-13 | 삼성전자주식회사 | Ink jet ink composition containing cyclic diether compound or cyclic dithiolan compound |
-
1981
- 1981-12-28 JP JP56214417A patent/JPS58116480A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58116480A (en) | 1983-07-11 |
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