JPH02264735A - Bromination of trialcohol - Google Patents
Bromination of trialcoholInfo
- Publication number
- JPH02264735A JPH02264735A JP8556589A JP8556589A JPH02264735A JP H02264735 A JPH02264735 A JP H02264735A JP 8556589 A JP8556589 A JP 8556589A JP 8556589 A JP8556589 A JP 8556589A JP H02264735 A JPH02264735 A JP H02264735A
- Authority
- JP
- Japan
- Prior art keywords
- dibromo
- organic solvent
- hydrobromic acid
- butanetriol
- butanol
- 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.)
- Pending
Links
- 230000031709 bromination Effects 0.000 title description 6
- 238000005893 bromination reaction Methods 0.000 title description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 21
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- PSSRAPMBSMSACN-UHFFFAOYSA-N 1,4-dibromobutan-2-ol Chemical compound BrCC(O)CCBr PSSRAPMBSMSACN-UHFFFAOYSA-N 0.000 claims abstract description 7
- JBVBFRXCWSBOOH-UHFFFAOYSA-N 1,5-dibromopentan-2-ol Chemical compound BrCC(O)CCCBr JBVBFRXCWSBOOH-UHFFFAOYSA-N 0.000 claims abstract description 6
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 13
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 238000010533 azeotropic distillation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000010992 reflux Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 abstract description 4
- 238000006297 dehydration reaction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000003791 organic solvent mixture Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- FVGBHSIHHXTYTH-UHFFFAOYSA-N pentane-1,1,1-triol Chemical compound CCCCC(O)(O)O FVGBHSIHHXTYTH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- -1 dibromo-2-pentanol Chemical compound 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N 2-pentanol Substances CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- CXYOZCOPUFGSKA-UHFFFAOYSA-N 3,3-dibromobutan-2-ol Chemical compound BrC(C(C)O)(C)Br CXYOZCOPUFGSKA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は１，２．４−ブタントリオール又は！、２．５
−ペンタントリオールの臭素化方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides 1,2,4-butanetriol or! , 2.5
- A method for brominating pentanetriol.
［従来の技術］
１．２．４−ブタントリオール又は１，２．５−ペンタ
ントリオールの第１級の水酸基を臭素化した部分臭素化
物は、ヘテロ環含有医薬等への有用な原料となる。従来
、これらのアルコールの部分臭素化方法については殆ど
報告が見当たらない。[Prior Art] Partially brominated products obtained by brominating the primary hydroxyl group of 1.2.4-butanetriol or 1,2.5-pentanetriol serve as useful raw materials for heterocycle-containing pharmaceuticals and the like. Hitherto, there have been almost no reports on methods for partial bromination of these alcohols.
アルコールの臭素化方法としてはガス状の臭化水素を用
いる方法と臭化水素酸（水溶液）を用いる方法が知られ
ているが、ガス状物での臭素化はボンベ等の使用が不可
欠となることから、−工業的には採用しがたいのが実情
であり、工業的規模での実施では臭化水素酸の使用か有
利であると言える。臭化水素酸を用いるアルコールの臭
素化法としては、例えばイソアミルアルコール等のアル
コールと臭化水素酸、及び硫酸（Ｏｒｇ ５ｙｎｔｈ
（１９４１）Ｃｏｉｌ Ｖｏｌ １ ２５−３１）や
酢酸（Ｊ 、Ｏｒｇ、Ｃｈｅｍ、３０．１９４５及び３
３０８ （１，９６５））等の酸を一括仕込みし、還流
させる方法や、特定のポリオールを有機酸の存在下で、
反応中に水を蒸留により除去しながら臭化水素水溶液と
反応させてブロモヒドリン類を製造する方法（特開昭５
８−４７３７号公報）が知られている。Methods for brominating alcohol include methods using gaseous hydrogen bromide and methods using hydrobromic acid (aqueous solution), but bromination using gaseous substances requires the use of cylinders, etc. Therefore, it is actually difficult to adopt it industrially, and it can be said that the use of hydrobromic acid is advantageous in implementation on an industrial scale. As a method for brominating alcohol using hydrobromic acid, for example, an alcohol such as isoamyl alcohol, hydrobromic acid, and sulfuric acid (Org 5ynth
(1941) Coil Vol 1 25-31) and acetic acid (J, Org, Chem, 30.1945 and 3
308 (1,965)) etc. in bulk and refluxing, or a method in which a specific polyol is added in the presence of an organic acid.
A method for producing bromohydrins by reacting with an aqueous hydrogen bromide solution while removing water by distillation during the reaction (Japanese Unexamined Patent Application Publication No. 5-117)
8-4737) is known.
［発明が解決しようとする課題］
しかし、本発明者の検討では従来行われている臭化水素
酸を用いる臭素化法では、１，２．４−ブタントリオー
ル又は１，２．５−ペンタントリオールを臭素化し、そ
れぞれ１，４−ジブロモ−２−ブタノール又は１．５−
ジブロモ−２−ペンタノールを製造しようとしても、反
応液がハルツ化する等のトラブルが多く、結果的に原料
アルコールからの目的物の収率が２０〜５０％程度と低
くなるため、工業的な実施では充分満足出来るものでは
ないことが明らかとなった。[Problems to be Solved by the Invention] However, according to the present inventor's study, the conventional bromination method using hydrobromic acid does not produce 1,2,4-butanetriol or 1,2,5-pentanetriol. 1,4-dibromo-2-butanol or 1,5-
Even when trying to produce dibromo-2-pentanol, there are many problems such as the reaction solution becoming harzic, and as a result, the yield of the target product from the raw alcohol is as low as 20-50%, making it difficult to produce industrially. It became clear that the implementation was not fully satisfactory.
［課題を解決するための手段］
そこで本発明者はかかる課題を解決するために鋭意研究
を行った結果、反応系への臭化水素酸の滴下仕込みと系
に共存する水の共沸除去の組合せにより該トリオールの
ジブロモ体が収率よく得られることを見出し、本発明を
完成するに至った。[Means for Solving the Problems] Therefore, as a result of intensive research to solve the problems, the inventors of the present invention found that the method of dropping hydrobromic acid into the reaction system and the azeotropic removal of water coexisting in the system. It was discovered that the dibromo form of the triol can be obtained in good yield by the combination, and the present invention was completed.
即ち本発明は、
ｒ １，２．４−ブタントリオール又は１，２．５−
ペンタントリオールを臭素化するにあたり、該トリオー
ルの有機溶媒分散液中に臭化水素酸を滴下し、水を共沸
除去しながら反応を行い、１．４−ジブロモ−２−ブタ
ノール又は１．５−ジブロモ−２−ペンタノールを得る
ことを特徴とするトリアルコールの臭素化方法。」であ
る。That is, the present invention provides r 1,2.4-butanetriol or 1,2.5-
When pentanetriol is brominated, hydrobromic acid is added dropwise to an organic solvent dispersion of the triol, and the reaction is carried out while water is azeotropically removed. A method for brominating trial alcohols, characterized in that dibromo-2-pentanol is obtained. ”.
本発明で使用する臭化水素酸の濃度は特に制限はないが
、通常、入手可能な２０〜５０重量％水溶液、特に容易
に商業的に入手可能な約４７重量％臭化水素酸が使用さ
れる。臭化水素酸の使用量は、理論量の２〜１０倍モル
を使用するのが適当である。The concentration of hydrobromic acid used in the present invention is not particularly limited, but typically an available 20 to 50% by weight aqueous solution, particularly a readily commercially available approximately 47% by weight hydrobromic acid, is used. Ru. The appropriate amount of hydrobromic acid to be used is 2 to 10 times the theoretical amount by mole.
有機溶媒としては、水と共沸し、かつ水とは相溶性を有
しないものが使用される。具体的？こはトルエン、ベン
ゼン、キシレン等、種々の溶媒が使用可能であるが、特
にトルエンを使用した場合にはよりハルツ分が少なく、
収率的にも有利である。使用量としては原料トリオール
１００重量部に対して２００〜６００重量部、好ましく
は３００〜５００重量部が実用的である。１００重量部
未満、及び８００重量部を超えるといずれも収率が低下
する。As the organic solvent, one that is azeotropic with water and has no compatibility with water is used. concrete? Various solvents can be used for this, such as toluene, benzene, xylene, etc., but especially when toluene is used, it has a lower Harz content.
It is also advantageous in terms of yield. The practical amount to be used is 200 to 600 parts by weight, preferably 300 to 500 parts by weight, per 100 parts by weight of the starting triol. If it is less than 100 parts by weight or more than 800 parts by weight, the yield will decrease.
本発明の反応は、まず上述のトリオールを有機溶媒に添
加し、撹拌混合しながら１０５〜１１５℃まで昇温し、
還流させる。ついでこの分散液に臭化水素酸を滴下する
。In the reaction of the present invention, first, the triol described above is added to an organic solvent, and the temperature is raised to 105 to 115°C while stirring and mixing.
Reflux. Hydrobromic acid is then added dropwise to this dispersion.
滴下に要する時間は使用する臭化水素酸の濃度により変
化するが、市販の約４７重量％臭化水素酸を使用した場
合は滴下時間は１〜２時間程度を要する。滴下終了後、
通常１〜２時間程度熟成させる。The time required for dropping varies depending on the concentration of hydrobromic acid used, but when commercially available hydrobromic acid of about 47% by weight is used, about 1 to 2 hours is required for dropping. After the dripping is finished,
It is usually aged for about 1 to 2 hours.
該反応液を冷却後、酢酸エチル等を用いて溶剤抽出し、
抽出液の溶媒を留去して目的の臭化アルコールを得る。After cooling the reaction solution, solvent extraction is performed using ethyl acetate etc.
The solvent of the extract is distilled off to obtain the desired alcohol bromide.
共沸で系から除去された水−有機溶媒混合液は二層分離
後、有機溶媒は反応溶媒として再使用される。The water-organic solvent mixture azeotropically removed from the system is separated into two layers, and the organic solvent is reused as a reaction solvent.
本発明の目的物である１、４−ジブロモ−２−ブタノー
ル及び１．５−ジブロモ−２−ペンタノールは、医薬等
の合成原料として産業上有用な化合物である。1,4-dibromo-2-butanol and 1,5-dibromo-2-pentanol, which are the objects of the present invention, are industrially useful compounds as raw materials for the synthesis of pharmaceuticals and the like.
［作 用］
本発明の臭素化方法においては、反応系への臭化水素酸
の滴下仕込みと水の共沸除去の組合わせによって、Ｉ。[Function] In the bromination method of the present invention, I.
２．４−ブタントリオール又は１，２．５−ペンタント
リオールからそれぞれ１．４−ジブロモ−２−ブタノー
ル又は１．５−ジブロモ−２−ペンタノールを得る際の
ハルツ化が防止でき、収率を向上させることができる。Harz formation can be prevented when obtaining 1.4-dibromo-2-butanol or 1.5-dibromo-2-pentanol from 2.4-butanetriol or 1,2.5-pentanetriol, respectively, and the yield can be improved. can be improved.
［実施例及び対照例コ 以下、実施例を挙げて本発明を更に具体的に説明する。[Example and control example Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
トルエン！００ｇと、１，２．４−ブタントリオール２
５、Ｏｇ（２３５，６ミリモル）を撹拌混合しながら、
１１０℃まで昇温し、還流状態番こした。この分散液に
４７重量％臭化水素酸４０５．５ｇ（２３５６ミリモル
）を約３時間かけて滴下すると共に共沸脱水を行いなが
ら、反応を継続した。滴下終了後、その状態で１時間熟
成を行った。室温まで冷却後、反応生成液に５重量％炭
酸ナトリウム水溶液１００ｇ及び酢酸エチル１００９を
加え抽出した。次に分取した酢酸エチル層を５重量％炭
酸ナトリウム溶液１００ｇで洗浄後、酢酸エチルを留去
し、１．４ジブロモ−２−ブタノール４４．３ｇを得た
。Example 1 Toluene! 00g and 1,2.4-butanetriol2
5. While stirring and mixing Og (235.6 mmol),
The temperature was raised to 110°C, and the mixture was kept under reflux. 405.5 g (2356 mmol) of 47% by weight hydrobromic acid was added dropwise to this dispersion over about 3 hours, and the reaction was continued while performing azeotropic dehydration. After the addition was completed, aging was carried out for 1 hour in that state. After cooling to room temperature, 100 g of a 5% by weight aqueous sodium carbonate solution and 1009 g of ethyl acetate were added to the reaction product solution for extraction. Next, the separated ethyl acetate layer was washed with 100 g of 5% by weight sodium carbonate solution, and then ethyl acetate was distilled off to obtain 44.3 g of 1.4 dibromo-2-butanol.
ガスクロマトグラフィー（以後、ＧＯと略記する）によ
るジベンジルエーテルを用いる内部標準法での分析の結
果、該アルコールの純度は９１．１％であり、収率は７
８．０％であった。As a result of analysis by internal standard method using dibenzyl ether by gas chromatography (hereinafter abbreviated as GO), the purity of the alcohol was 91.1%, and the yield was 7.
It was 8.0%.
対照例１
実施例１と同量のトルエン、１，２．４−ブタントリオ
ール及び臭化水素酸を一括仕込み後、撹拌しながら１０
０℃まで昇温し、共沸脱水下に還流状態で５時間反応を
行った。この反応液を室温まで冷却したところ、多量の
ハルツ分が観測された。以後、実施例１と同様に後処理
を行い、１．４−ジブロモ−２−ブタノール４０．０９
を得ノご。Control Example 1 After charging the same amounts of toluene, 1,2,4-butanetriol and hydrobromic acid as in Example 1, the mixture was heated for 10 minutes with stirring.
The temperature was raised to 0°C, and the reaction was carried out under reflux for 5 hours under azeotropic dehydration. When this reaction solution was cooled to room temperature, a large amount of Hartz was observed. Thereafter, post-treatment was carried out in the same manner as in Example 1, and 1,4-dibromo-2-butanol 40.09
Get it.
ＧＣによる分析の結果、純度５２．８％であり、収率は
４８．４％であった。As a result of GC analysis, the purity was 52.8% and the yield was 48.4%.
対照例２
１．２．４−ブタントリオール２５．０９（２３５，６
ミリモル）を撹拌しながら１１０℃まで昇温し、４７重
量％臭化水素酸４０５．５９Ｃ２３５６ミリモル）を約
３時間かけて滴下した。滴下終了後、その状態で１時間
熟成を行った。この反応液を室温まで冷却したところ、
多量のハルツ分が観測された。以後、実施例１と同様に
後処理を行い、■、４−ジブロモ−２−ブタノール２２
．７９を得た。Control example 2 1.2.4-butanetriol 25.09 (235,6
The mixture was heated to 110° C. with stirring, and 47% by weight hydrobromic acid (405.59C, 2356 mmol) was added dropwise over about 3 hours. After the addition was completed, aging was carried out for 1 hour in that state. When this reaction solution was cooled to room temperature,
A large amount of Hartz fraction was observed. Thereafter, post-treatment was carried out in the same manner as in Example 1, and ■,4-dibromo-2-butanol 22
．． I got 79.
ＧＣによる分析の結果、純度２９．２％であり、収率は
２０．２％であった。As a result of GC analysis, the purity was 29.2% and the yield was 20.2%.
対照例３
１．２．４−ブタントリオール２５．Ｏｇ（２３５，６
ミリモル）４７重里％臭化水素酸８６．１ｙ（５００ミ
リモル）及び酢酸２ｇを混合し、９５〜１００℃に昇温
し７時間にわたって水を蒸留除去しながら反応を行った
。反応終了液を真空蒸留した結果４２．０ｇの１．４−
ジブロモ−２−ブタノールを得た。Control Example 3 1.2.4-Butanetriol 25. Og(235,6
86.1y (500 mmol) of 47% hydrobromic acid and 2 g of acetic acid were mixed, heated to 95-100°C, and reacted over 7 hours while distilling off water. As a result of vacuum distillation of the reaction completed liquid, 42.0 g of 1.4-
Dibromo-2-butanol was obtained.
ＧＯによる分析の結果、純度４３．７％であり、収率は
３３．６％であった。As a result of GO analysis, the purity was 43.7%, and the yield was 33.6%.
実施例２
１．２．４−ブタントリオールの代わりに１．２．５−
ペンタントリオール３０．０９（２５０ミリモル）を使
用する以外は、実施例Ｉに準じて実験を行った。Example 2 1.2.5-instead of 1.2.4-butanetriol
The experiment was carried out according to Example I, except that 30.09 (250 mmol) of pentanetriol was used.
ＧＣ分析により１．５−ジブロモ−２−ペンタノールが
純度９２％、収率は７５．０％で得られたことが認めら
れた。GC analysis confirmed that 1,5-dibromo-2-pentanol was obtained with a purity of 92% and a yield of 75.0%.
対照例４
１．２．４−ブタントリオールの代わりに１．２．５−
ペンタントリオール３０．０ｙ（２５０ミリモル）を使
用する以外は、対照例１に準じて実験を行った。Control example 4 1.2.5-instead of 1.2.4-butanetriol
An experiment was conducted according to Control Example 1 except that 30.0y (250 mmol) of pentanetriol was used.
ＧＯ分析により１．５−ジブロモ−２−ペンタノールが
純度３５．５％、収率は４３．０％であった。GO analysis showed that 1,5-dibromo-2-pentanol had a purity of 35.5% and a yield of 43.0%.
［効 果］
前記の如く本発明の臭素化方法は、反応系への臭化水素
酸の滴下仕込みと水の共沸除去の組合わせを採用するこ
とにより、１，２．４−ブタントリオール又は１．２．
５ペンタントリオールからそれぞれ１．４−ジブロモ−
２−ブタノール又は１．５−ジブロモ−２−ペンタノー
ルを収率よく得、ることかできる。[Effect] As described above, the bromination method of the present invention employs a combination of dropping hydrobromic acid into the reaction system and azeotropic removal of water, thereby producing 1,2,4-butanetriol or 1.2.
5-pentanetriol to 1,4-dibromo-
2-butanol or 1,5-dibromo-2-pentanol can be obtained in good yield.
Claims (1)
ンタントリオールを臭素化するにあたり、該トリオール
の有機溶媒分散液中に臭化水素酸を滴下し、水を共沸除
去しながら反応を行い、１，４−ジブロモ−２−ブタノ
ール又は１，５−ジブロモ−２−ペンタノールを得るこ
とを特徴とするトリアルコールの臭素化方法。 ２、有機溶媒がトルエンであることを特徴とする特許請
求の範囲第１項記載の製造方法。[Claims] When brominating 1,1,2,4-butanetriol or 1,2,5-pentanetriol, hydrobromic acid is added dropwise to an organic solvent dispersion of the triol, and water is removed. 1. A method for brominating trial alcohols, characterized in that the reaction is carried out with azeotropic removal to obtain 1,4-dibromo-2-butanol or 1,5-dibromo-2-pentanol. 2. The manufacturing method according to claim 1, wherein the organic solvent is toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8556589A JPH02264735A (en) | 1989-04-03 | 1989-04-03 | Bromination of trialcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8556589A JPH02264735A (en) | 1989-04-03 | 1989-04-03 | Bromination of trialcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02264735A true JPH02264735A (en) | 1990-10-29 |
Family
ID=13862335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8556589A Pending JPH02264735A (en) | 1989-04-03 | 1989-04-03 | Bromination of trialcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02264735A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7126007B2 (en) | 2003-11-28 | 2006-10-24 | L'oreal S.A. | Process for preparing pyrrolidinyl-functional para-phenylenediamine derivatives substituted by a nitrogenous radical, and intermediate compounds |
-
1989
- 1989-04-03 JP JP8556589A patent/JPH02264735A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7126007B2 (en) | 2003-11-28 | 2006-10-24 | L'oreal S.A. | Process for preparing pyrrolidinyl-functional para-phenylenediamine derivatives substituted by a nitrogenous radical, and intermediate compounds |
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