JPS593993B2 - Method for producing isothiocyanate derivatives - Google Patents
Method for producing isothiocyanate derivativesInfo
- Publication number
- JPS593993B2 JPS593993B2 JP1946976A JP1946976A JPS593993B2 JP S593993 B2 JPS593993 B2 JP S593993B2 JP 1946976 A JP1946976 A JP 1946976A JP 1946976 A JP1946976 A JP 1946976A JP S593993 B2 JPS593993 B2 JP S593993B2
- Authority
- JP
- Japan
- Prior art keywords
- acetyl
- gluconyl
- mol
- penta
- isothiocyanate
- 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
- 150000002540 isothiocyanates Chemical class 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- RHUVFRWZKMEWNS-UHFFFAOYSA-M silver thiocyanate Chemical compound [Ag+].[S-]C#N RHUVFRWZKMEWNS-UHFFFAOYSA-M 0.000 claims description 10
- 150000004820 halides Chemical class 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、イソチオシアネート誘導体の製造法１５に関
し、その主旨とするところは、式（■）
ＡｃＯ（■）
（但しＡｃはアセチル基を、Ｘはハロゲンを表わす）で
表わされる２・３・４・５・６−ペンメ−０−アセチル
−Ｄ−グルコニルハライドにチオシアン３０酸銀を作用
させることを特徴とする式（Ｉ）’
３５Ａ肝￥ （）
（但しＡｃは前記と同じ意味である）
で表わされる２・３・４・５・６−ペンタ−０−アセチ
ル−Ｄ−グルコニルイソチオシアネートの製造法である
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to method 15 for producing isothiocyanate derivatives, the gist of which is that the formula (■) AcO (■) (where Ac represents an acetyl group and X represents a halogen) Formula (I)' 35A liver () (where Ac is This is a method for producing 2,3,4,5,6-penta-0-acetyl-D-gluconyl isothiocyanate, which has the same meaning as above.
本発明者らは、糖のイソチオシアネート誘導体の研究を
行つて来たが、次の一般式（１）（但しＲは、２・３・
４・５・６−ペンタ−Ｄ−アセチル−Ｄ−グルコニル基
、２・３・５−トリ０−ベンゾイル−β−Ｄ−リボフラ
ノシル基、２・３・４・６−テトラ−０−アセチル−β
−Ｄ−グルコピラノシル基、２・３・４−トリ−０アセ
チル−α−Ｄ−アラビノピラノシル基から選ばれた置換
基を表わす）で表わされる化合物が種種の新規化合物の
合成に有用であることを発見した。The present inventors have been conducting research on isothiocyanate derivatives of sugars, and have found the following general formula (1) (where R is 2, 3,
4,5,6-penta-D-acetyl-D-gluconyl group, 2,3,5-tri0-benzoyl-β-D-ribofuranosyl group, 2,3,4,6-tetra-0-acetyl-β
-D-glucopyranosyl group, 2,3,4-tri-0acetyl-α-D-arabinopyranosyl group) are useful for the synthesis of various new compounds. I discovered something.
本発明者は、この式（１）に示される化合物のうち特に
、２・３・４・５・６−ベンツ−０−アセチル−Ｄ−グ
ルコニルイソチオシアネート（１）１が２・３・４・５
・６−ペンタ−０−アセチル−Ｄ−グルコニルハライド
（）にチオシアン酸塩のうち特にチオシアン酸銀を作用
させることによつて効率的に得られることを発見し、本
発明を完成させた。Among the compounds represented by the formula (1), the present inventors particularly discovered that 2,3,4,5,6-benz-0-acetyl-D-gluconyl isothiocyanate (1) 1 is 2,3,4・5
- It was discovered that it can be efficiently obtained by reacting 6-penta-0-acetyl-D-gluconyl halide () with thiocyanates, especially silver thiocyanate, and the present invention was completed.
式（１）で示される化合物は、例えば特願昭４９−２５
１０８号、同４９−１１１６３１号の発明の出発物質と
して重要である。The compound represented by the formula (1) is, for example,
It is important as a starting material for the inventions of No. 108 and No. 49-111631.
次に本発明の方法によつて得られる化合物である２・３
・４・５・６−ベンダー０−アセチルＤ−グルコニルイ
ソチオシアネートの物性値はＭｐ．：１３２〜１３５℃
、Ｒ（？−り：１９８０（ＮＣＳ）、１７４０（エステ
ル）である。Next, compounds 2 and 3 obtained by the method of the present invention
・The physical property values of 4, 5, 6-bender 0-acetyl D-gluconyl isothiocyanate are Mp. :132~135℃
, R(?-ri: 1980 (NCS), 1740 (ester).
次に本発明の方法をさらに具体的に説明する。Next, the method of the present invention will be explained in more detail.
本発明は次の式で表わされる２・３・４・５・６−ペン
タ−０アセチル−Ｄ−グルコニルハライドにチオシアン
酸銀を作用させることにより行われる。The present invention is carried out by reacting 2,3,4,5,6-penta-0acetyl-D-gluconyl halide represented by the following formula with silver thiocyanate.
反応は、ベンゼン、キシレン、シクロヘキサン等反応に
不活性な溶媒に溶解して行ない、温度は５０〜１５０℃
、反応時間は１時間〜１０時間が適当である。The reaction is carried out by dissolving in a solvent inert to the reaction such as benzene, xylene, cyclohexane, etc., and the temperature is 50 to 150°C.
A suitable reaction time is 1 hour to 10 hours.
反応終了後放冷してろ過し目的物を得るが石油エーテル
、メ汐ノール、エタノール等を加えて結晶を析出させる
こともできる。かくして式（ＩＸで表わされる２・３・
４・５・６−ペンタ−０アセチル−Ｄ−グルコニルイソ
チオシアネートを得ることができる。After the reaction is completed, the desired product is obtained by cooling and filtering, but it is also possible to precipitate crystals by adding petroleum ether, methanol, ethanol, etc. Thus, the formula (2, 3, represented by IX)
4,5,6-penta-0 acetyl-D-gluconyl isothiocyanate can be obtained.
本発明の出発物質である式（）で示される化合物は、対
応する糖にチオニルクロライド、五塩化リン、臭素等を
作用させるか、あるいはエステル化（アセチル化、ベン
ゾイル化等）、エーテル化（アルキル、アリール、その
他）を行つた後ハロゲン化水素を反応させることによつ
て製造することができる。The compound represented by formula (), which is the starting material of the present invention, can be prepared by reacting the corresponding sugar with thionyl chloride, phosphorus pentachloride, bromine, etc. , aryl, etc.) and then reacting with hydrogen halide.
次に実施例により本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例
２・３・４・５・６−ペンタ−０−アセチルＤ−グルコ
ニルイソチオシアネートの製造２・３・４・５・６−ペ
ンタ−０−アセチルＤ−グルコニルクロライド９７（０
．０２モル）を無水キシレン２００ｍ１に溶解しチオシ
アン酸銀３．３ｙ（０．０２モル）を加えた。Example 2, 3, 4, 5, 6-Penta-0-acetyl D-gluconyl isothiocyanate production 2, 3, 4, 5, 6-penta-0-acetyl D-gluconyl chloride 97 (0
．． 02 mol) was dissolved in 200 ml of anhydrous xylene, and 3.3 y (0.02 mol) of silver thiocyanate was added.
徐々に３０分間かけ９０〜１００２にし１時間加熱攪拌
後、さらにチオシアン酸銀１．７７（０．０１モル）を
加えた。５時間加熱攪拌後放冷しろ過し、ろ液に石油エ
ーテル３００ｍ１注ぎ一夜冷所に放置した。The mixture was gradually brought to 90 to 1002 over 30 minutes with stirring for 1 hour, and then 1.77 (0.01 mol) of silver thiocyanate was added. After heating and stirring for 5 hours, the mixture was allowed to cool and filtered, and the filtrate was poured with 300 ml of petroleum ether and left in a cool place overnight.
無色針状晶７．５７（８８％）をえた。Ｍｐ．：１３２
〜１３５えＣ
ＩＲ（Ｃｍ−り：１９８０（ＮＣＳ）、１７４０（エス
テル）本方法は、鎖状の化合物以外にも例えば含酸素複
素環基を含むハライドについても適用できるのでその方
法は参考例として記した。7.57 (88%) of colorless needle crystals were obtained. Mp. :132
~135E C IR (Cm-Re: 1980 (NCS), 1740 (ester)) This method can be applied not only to chain compounds but also to halides containing oxygen-containing heterocyclic groups, so this method is used as a reference example. I wrote it down.
参考例 １
２・３・５−トリ−０−ベンゾイル−β−Ｄリボフラノ
シルイソチオシアネートの製造窒素気流中、２・３・５
−トリ−０−ベンゾイル−β−Ｄ−リボフラノシルプロ
マイド５７（０．０１モル）を無水キシレン１００ｍ１
に溶解させ、チオシアン酸銀２ｙ（０．０１モル）を加
え徐徐に３０分間で９０〜９５０にした。Reference example 1 Production of 2,3,5-tri-0-benzoyl-β-D ribofuranosyl isothiocyanate In a nitrogen stream, 2,3,5
-Tri-0-benzoyl-β-D-ribofuranosyl bromide 57 (0.01 mol) in 100 ml of anhydrous xylene
Silver thiocyanate 2y (0.01 mol) was added thereto and the concentration was gradually adjusted to 90 to 950 over 30 minutes.
さらにチオシアン酸銀１７（０，００６モル）加え２〜
３時間、同一温度で攪拌後放冷しろ過後、ろ液を減圧下
水浴土（６０〜７００）で濃縮しシロツプ４．３ｙ（９
０％）をえた。Ｍｐ．：９９〜１００℃
ＩＲ（Ｃｍ−１）：２０００（ＮＣＳ）、１７２０（エ
ステル）。Furthermore, silver thiocyanate 17 (0,006 mol) was added to 2~
After stirring at the same temperature for 3 hours, cooling and filtration, the filtrate was concentrated under reduced pressure with water bath soil (60-700) to give a syrup of 4.3y (90%).
0%). Mp. : 99-100°C IR (Cm-1): 2000 (NCS), 1720 (ester).
参考例 ２
２・３・４・６−テトラ−０−アセチル−βＤ−グルコ
ピラノシルイソチオシアネートの製造窒素気流中２・３
・４・６−テトラ−０−アセチル−β−Ｄ−グルコピラ
ノシルプロマイド４．５７（０．０１モル）を無水キシ
レン１００ｍ１に溶解しチオシアン酸銀４．５７（０．
０３モル）を加えてから３０分間で９０〜１０００にし
たのちさらにチオシアン酸銀１，６７（０．０１モル）
を加え３時間加熱攪拌をした。Reference Example 2 Production of 2,3,4,6-tetra-0-acetyl-βD-glucopyranosylisothiocyanate 2,3 in nitrogen stream
- 4.57 (0.01 mol) of 4,6-tetra-0-acetyl-β-D-glucopyranosyl bromide was dissolved in 100 ml of anhydrous xylene, and 4.57 (0.01 mol) of silver thiocyanate was dissolved.
After adding 0.03 mol) to 90-1000 in 30 minutes, add 1,67 (0.01 mol) of silver thiocyanate.
was added and heated and stirred for 3 hours.
放冷後ろ過しろ液に石油エーテル４００ｍ１を加え、冷
所に一夜放置し無色針状晶を３．７７（８６％）えた。
Ｍｐ．：１１３〜１１５えＣ
ＩＲ（？−１）：２１００（ＮＣＳ）、１７４０（エス
テル）。After cooling, 400 ml of petroleum ether was added to the filtered filtrate and left in a cool place overnight to yield 3.77 (86%) colorless needle crystals.
Mp. :113-115eC IR (?-1): 2100 (NCS), 1740 (ester).
参考例 ３
２・３・４−トリ−０−アセチル−α−Ｄ−アラビノピ
ラノシルイソチオシアネートの製造窒素気流中２・３・
４−トリ−０−アセチルα−Ｄ−アラビノピラノシルプ
ロマイド６．２ｙ（０．０２モル）を無水キシレン１０
０ｍ１に溶解しチオシアン酸銀３．３７（０．０２モル
）を加え３６０分間で徐々に加熱し９０〜１００２にし
た。Reference Example 3 Production of 2,3,4-tri-0-acetyl-α-D-arabinopyranosyl isothiocyanate 2,3,4 in nitrogen stream
6.2y (0.02 mol) of 4-tri-0-acetyl α-D-arabinopyranosyl bromide was added to 10% of anhydrous xylene.
3.37 (0.02 mol) of silver thiocyanate was added to the solution and gradually heated over 360 minutes to give a concentration of 90 to 100.
Claims (1)
表わされる２・３・４・５・６−ペンタ−Ｏ−アセチル
−Ｄ−グルコニルハライドにチオシアン酸銀を作用させ
ることを特徴とする式 ▲数式、化学式、表等があります▼ （但しＡｃは前記と同じ意味である） で表わされる２・３・４・５・６−ペンタ−Ｏ−アセチ
ル−Ｄ−グルコニルイソチオシアネートの製造法。[Claims] 1 2,3,4,5,6-penta-O-acetyl represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (where Ac represents an acetyl group and X represents a halogen) Formulas characterized by the action of silver thiocyanate on -D-gluconyl halide ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Ac has the same meaning as above) 2, 3, 4, 5 expressed by - A method for producing 6-penta-O-acetyl-D-gluconyl isothiocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1946976A JPS593993B2 (en) | 1976-02-26 | 1976-02-26 | Method for producing isothiocyanate derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1946976A JPS593993B2 (en) | 1976-02-26 | 1976-02-26 | Method for producing isothiocyanate derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52105123A JPS52105123A (en) | 1977-09-03 |
| JPS593993B2 true JPS593993B2 (en) | 1984-01-27 |
Family
ID=12000167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1946976A Expired JPS593993B2 (en) | 1976-02-26 | 1976-02-26 | Method for producing isothiocyanate derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS593993B2 (en) |
-
1976
- 1976-02-26 JP JP1946976A patent/JPS593993B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52105123A (en) | 1977-09-03 |
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