TW480254B - Process for preparing 3-(hydroxymethyl) chromen-4-ones - Google Patents
Process for preparing 3-(hydroxymethyl) chromen-4-ones Download PDFInfo
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- TW480254B TW480254B TW088115637A TW88115637A TW480254B TW 480254 B TW480254 B TW 480254B TW 088115637 A TW088115637 A TW 088115637A TW 88115637 A TW88115637 A TW 88115637A TW 480254 B TW480254 B TW 480254B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
經濟部智慧財產局員工消費合作社印製 480254 A7 B7 五、發明說明(/) 本發明係有關一種製備通式I 3-(羥甲基)色原烯-4-酮 類之新穎方法:
其中R爲氫,鹵素,具有1至4個碳原子的烷基或具有丄 至4個碳原子之烷氧基,視情況經苯基或鹵素取代之烷氧 基。 本發明化合物可用爲製備醫藥品中之中間體,例如該 等在台灣專利第101549號(公報第353071號)中所揭示者。 用於製備通式I化合物之方法包括: a) 對應的3-甲醯基色原烯-4-酮類與NaBH4和AlCh之 速原作用(Tetrahedron Letters,1973, 1995; Tetrahedron,1974, 3〇, 3553; Chem. Pharm. Bull., 1974, 0,2959)。彼等反應具 有導致低產率之不利處。 b) 對應的2-亞磺醯基苯乙酮(2-su€finyl acetophenones) 與二莫耳的HCH0之縮合作用及隨後亞硼之熱解作用(J. Het· Chem·,UM,U,183)。不幸地,在以工業規模製備亞 磺醯基苯乙酮時會有爆炸之危險。 本發明之方法包括使用甲醛和催化量的鹼性化合物, 例如乙酸鈉,處理通式Π之化合物;其中R如⑴所定義, 接著在酸性介質中脫水。可用常用的礦物酸,例如鹽酸作 爲酸化劑。 3 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---------_裝---- (請先閱讀背面之注意事項再填寫本頁) 訂---------% 480254 A7 B7 五、發明說明(>) 通式π化合物經發現會與彼等的開環互變異構% Π ”平衡存在著(Tetrahedron Letters,1984. 25.^ 5813) 和Π”兩者之中R皆如前述構造所定義。
Ο 0H
CHO II1
ΙΓ 與先前所述諸方法相反,本發明方法可提供高__ 此外,前驅體的工業製備可以容易地進行。 + 經濟部智慧財產局員工消費合作社印製 實施侃丄:2-羥基-色原烯-4-酮類 於氮氣大氣下,將3.25克(60毫莫耳)甲醇鈉懸浮在經 冷却到0°C的60毫升甲酸乙酯中。使該混合物達到室溫^ ,滴加對應的鄰-羥基苯乙酮ΠΙ(20毫莫耳),其中R如前述 構造所定義,在最少量四氫呋喃中之溶液。將該混合物攪 拌30分鐘形成一濃黏糊。加入100毫升水和4.5毫升乙酸 並攪拌10分鐘’溶解掉沈澱物。將有機相傾出並用另40 毫升甲酸乙酯移去水相。將合倂的有機萃取液用兩份40毫 升碳酸氫鈉飽和溶液萃洗滌,經無水硫酸鈉脫水再予以蒸 發至乾。將剩餘物懸浮於40毫升異丙醚中,過瀘並在真空 中乾燥而得通式Π化合物。 :·裝--------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 480254 A7 B7 五、發明說明(> )
R(n) 產率(%) Μ·Ρ·° (DSC) Η 87 88.30 6-CH3 100 136.03 7-OCH3 85 139.44 6-OCH3 92 146.61 6-C1 93 160.62 7-〇CH2ph 92 172.63 7-〇(CH2)3Cl 80 118.23 7-0(CH2)sBr 69 104.95 (請先閱讀背面之注意事項再填寫本頁)
實施例2 : 3-(羥甲基)色原烯-4-酮I 經濟部智慧財產局員工消費合作社印製 於10毫莫耳Π在40毫升丙酮中的溶液內,加入40毫 克(0.5毫莫耳)乙酸鈉和1毫升之37%甲醛(12毫莫耳)並在 室溫下攪拌12小時。於該溶液中,加入1毫升濃鹽酸並在 室溫下攪拌整個晚上。用乙酸鈉水溶液中和該溶液,及於 真空中蒸發至乾。加入50毫升水後,用2份各50毫升的 乙酸乙酯萃取。將有機萃取液以無水硫酸鈉脫水並濃縮到 約15毫升之體積。將所得產物靜置於冰箱中整個晚上使其 結晶後,過濾收集。濾液用乙酸乙酯洗滌及真空乾燥而得 通式I化合物。
本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 480254 A7 B7 五、發明說明(f ) R(n) Η 6- CH3 7- OCH3 6-OCH3 6- C1 7- 〇CH2ph 7-〇(CH2)3Cl 7-〇(CH2)3Br 產率(%) Μ·Ρ·。(DSC) 82 109.3 70 143.7 78 119.98 80 151.8 71 164.27 70 135.9 75 101.77 75 105.38 (請先閱讀背面之注意事項再填寫本頁) ---------訂 *--------座 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)
Claims (1)
- 480254 B8 Co D8 α〇- η " 口 /十、. { / 六、申請專利乾圍 ί 07 1.一種製備通式I的3-(羥甲基)色原烯-4-酮類之方法:(請先閱讀背面之注意事項再填寫本頁) 其中R爲氫,鹵素,具有1至4個碳原子的烷基或有1至 4個碳原子的烷氧基,視情況經苯基或鹵素取代;其特徵 |在使用於丙酮中之甲醛與鹼性催化劑在室溫下處理如下通 Ϊ式Π之2-羥基-色原烯-4酮, r.' Γ ΟC接著在室溫下於酸性介質中脫水,接著以乙酸鈉水溶液中 ^和且在真空下蒸發至乾燥,然後力口入水及乙酸乙酯、萃取 、乾燥、濃縮並結晶。 經濟部智慧財產局員工消費合作社印製 2. 如申請專利範圍第1項之方法,其中係使用乙酸鈉 作爲鹼性催化劑。 3. 如申請專利範圍第1項之方法,其中係使用礦物酸 作爲酸性介質。 4. 如申請專利範圍第2項之方法,其中係使用鹽酸作 爲酸性介質。 . 1 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES009801970A ES2154176B1 (es) | 1998-09-21 | 1998-09-21 | Nuevo procedimiento de obtencion de 3-(hidroximetil)cromen-4-onas. |
Publications (1)
Publication Number | Publication Date |
---|---|
TW480254B true TW480254B (en) | 2002-03-21 |
Family
ID=8305211
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW088115637A TW480254B (en) | 1998-09-21 | 1999-09-10 | Process for preparing 3-(hydroxymethyl) chromen-4-ones |
Country Status (19)
Country | Link |
---|---|
US (1) | US6348605B1 (zh) |
EP (1) | EP1115717B1 (zh) |
JP (1) | JP3983979B2 (zh) |
KR (1) | KR100547939B1 (zh) |
AR (1) | AR017003A1 (zh) |
AT (1) | ATE261437T1 (zh) |
AU (1) | AU754043B2 (zh) |
BR (1) | BR9914009B1 (zh) |
CA (1) | CA2344664C (zh) |
DE (1) | DE69915498T2 (zh) |
DK (1) | DK1115717T3 (zh) |
ES (1) | ES2154176B1 (zh) |
IL (1) | IL141751A (zh) |
NO (1) | NO327046B1 (zh) |
NZ (1) | NZ510309A (zh) |
PT (1) | PT1115717E (zh) |
TW (1) | TW480254B (zh) |
WO (1) | WO2000017183A1 (zh) |
ZA (1) | ZA995877B (zh) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2378573A (en) | 1939-07-08 | 1945-06-19 | Natta Giulio | Process for the manufacture of keto-alcohols |
US3887584A (en) * | 1972-11-24 | 1975-06-03 | Warner Lambert Co | 3-(Hydroxymethyl)chromones |
IL112764A0 (en) | 1994-03-18 | 1995-05-26 | Ferrer Int | New chromene derivatives |
ES2101620B1 (es) * | 1994-03-18 | 1998-04-01 | Ferrer Int | Nuevo compuesto derivado del cromeno. |
ES2101646B1 (es) * | 1995-04-12 | 1998-04-01 | Ferrer Int | Nuevo compuesto derivado del cromeno. |
-
1998
- 1998-09-21 ES ES009801970A patent/ES2154176B1/es not_active Expired - Fee Related
-
1999
- 1999-09-10 TW TW088115637A patent/TW480254B/zh not_active IP Right Cessation
- 1999-09-13 ZA ZA9905877A patent/ZA995877B/xx unknown
- 1999-09-13 AR ARP990104580A patent/AR017003A1/es active IP Right Grant
- 1999-09-20 AT AT99953745T patent/ATE261437T1/de active
- 1999-09-20 KR KR1020017003562A patent/KR100547939B1/ko not_active IP Right Cessation
- 1999-09-20 JP JP2000574093A patent/JP3983979B2/ja not_active Expired - Fee Related
- 1999-09-20 DK DK99953745T patent/DK1115717T3/da active
- 1999-09-20 EP EP99953745A patent/EP1115717B1/en not_active Expired - Lifetime
- 1999-09-20 WO PCT/EP1999/006946 patent/WO2000017183A1/en active IP Right Grant
- 1999-09-20 PT PT99953745T patent/PT1115717E/pt unknown
- 1999-09-20 NZ NZ510309A patent/NZ510309A/en not_active IP Right Cessation
- 1999-09-20 DE DE69915498T patent/DE69915498T2/de not_active Expired - Lifetime
- 1999-09-20 BR BRPI9914009-8A patent/BR9914009B1/pt not_active IP Right Cessation
- 1999-09-20 IL IL14175199A patent/IL141751A/xx not_active IP Right Cessation
- 1999-09-20 AU AU10331/00A patent/AU754043B2/en not_active Ceased
- 1999-09-20 CA CA002344664A patent/CA2344664C/en not_active Expired - Fee Related
- 1999-09-20 US US09/787,113 patent/US6348605B1/en not_active Expired - Fee Related
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2001
- 2001-03-20 NO NO20011401A patent/NO327046B1/no not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JP2002526487A (ja) | 2002-08-20 |
CA2344664C (en) | 2006-11-07 |
NZ510309A (en) | 2002-06-28 |
NO20011401D0 (no) | 2001-03-20 |
AU754043B2 (en) | 2002-10-31 |
NO20011401L (no) | 2001-03-20 |
PT1115717E (pt) | 2004-07-30 |
AU1033100A (en) | 2000-04-10 |
DE69915498T2 (de) | 2004-08-19 |
DE69915498D1 (de) | 2004-04-15 |
IL141751A (en) | 2005-03-20 |
AR017003A1 (es) | 2001-08-22 |
CA2344664A1 (en) | 2000-03-30 |
ZA995877B (en) | 2001-01-02 |
BR9914009A (pt) | 2001-07-03 |
DK1115717T3 (da) | 2004-07-12 |
NO327046B1 (no) | 2009-04-14 |
JP3983979B2 (ja) | 2007-09-26 |
WO2000017183A1 (en) | 2000-03-30 |
BR9914009B1 (pt) | 2010-02-09 |
EP1115717B1 (en) | 2004-03-10 |
KR100547939B1 (ko) | 2006-02-02 |
IL141751A0 (en) | 2002-03-10 |
US6348605B1 (en) | 2002-02-19 |
ES2154176B1 (es) | 2001-10-16 |
KR20010075229A (ko) | 2001-08-09 |
ES2154176A1 (es) | 2001-03-16 |
ATE261437T1 (de) | 2004-03-15 |
EP1115717A1 (en) | 2001-07-18 |
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