GB2027425A - Glutaric Acid and Anhydride Derivatives - Google Patents

Glutaric Acid and Anhydride Derivatives Download PDF

Info

Publication number
GB2027425A
GB2027425A GB7921396A GB7921396A GB2027425A GB 2027425 A GB2027425 A GB 2027425A GB 7921396 A GB7921396 A GB 7921396A GB 7921396 A GB7921396 A GB 7921396A GB 2027425 A GB2027425 A GB 2027425A
Authority
GB
United Kingdom
Prior art keywords
compound
accordance
acid
formula
glutaric
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
Application number
GB7921396A
Other versions
GB2027425B (en
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ER Squibb and Sons LLC
Original Assignee
ER Squibb and Sons LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US05/901,952 external-priority patent/US4230621A/en
Application filed by ER Squibb and Sons LLC filed Critical ER Squibb and Sons LLC
Publication of GB2027425A publication Critical patent/GB2027425A/en
Application granted granted Critical
Publication of GB2027425B publication Critical patent/GB2027425B/en
Expired legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/74—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving hormones or other non-cytokine intercellular protein regulatory factors such as growth factors, including receptors to hormones and growth factors
    • G01N33/743—Steroid hormones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J19/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 by a lactone ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
    • C07J5/0046—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond substituted in position 17 alfa
    • C07J5/0053—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond substituted in position 17 alfa not substituted in position 16
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
    • C07J71/0005—Oxygen-containing hetero ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Urology & Nephrology (AREA)
  • Immunology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hematology (AREA)
  • Biomedical Technology (AREA)
  • Biochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Biotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Cell Biology (AREA)
  • Endocrinology (AREA)
  • Microbiology (AREA)
  • Steroid Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A compound having the formula <IMAGE> wherein R is hydrogen or an alkyl group having 1 to 3 carbon atoms; R1 is alkanoyl having 2 to 6 carbon atoms and n is 0, 1, 2, 3 or 4, and the corresponding acids where n NOTEQUAL 0 and R1 is methyl or hydrogen may be used as intermediates in the preparation of steroid compounds.

Description

1
GB 2 027 425 A 1
SPECIFICATION
Glutaric Acid and Anhydride Derivatives
This invention relates to glutaric acid and anhydride derivatives.
According to one aspect of the invention there is provided a compound having the formula
/ V-(0Hj)n
CH
°^c wherein R is hydrogen or an alkyl grouphaving 1 to 3 carbon atoms; R, is alkanoyl having 2 to 6 10 carbon atoms and n is 0, 1, 2, 3 or 4.
According to another aspect of the invention there is provided a compound having the formula
(0H.)„
0
jiHj-I-OH
wherein R is hydrogen or an alkyl group having 1 15 to 3 carbon atoms and n is 1, 2, 3 or 4.
According to a further aspect of the invention there is provided a compound having the formula
OHj-C-OH _CH
wherein R is hydrogen or alkyl having 1 to 3 20 carbon atoms and n is 1, 2, 3 or 4.
These compounds may be used in the synthesis of steroids in accordance with our patent application No. 33217/78. Serial No. 2002385.
25 In Formula I R, is preferably acetyl.
The compounds of Formula I can be prepared by first reacting 4-methoxyphenylaliphatic aldehyde having the formula
IV
(CH2)n-^H
30 with at least 2 molar equivalents of cyanoacetic acid in the presence of a base (e.g., sodium hydroxide) to yield, on acid hydrolyisis, a compound having the formula
V
CBjO
0
pHg-l-OH
L-o,
glutaric acid can be accomplished with boiling alcoholic sodium hydroxide solution.
45 Demethylation of the glutaric acid derivatives of formula V results in glutaric acid derivatives having the formula
35 An alternative preparation for the compound of formula V wherein n is 0 and R is hydrogen, i.e., 3-(4-methoxyphenyl) glutaric acid, is disclosed by Smith et al., J.A.C.S., 72, 1877 (1950). In that procedure, anisaldehyde is condensed with ethyl 40 acetoacetate in the presence of piperidine to give ethyl anisal-bis- acetoacetate. Cleavage of the product to give the desired 3-(4-methoxyphenyl)
VI
r\
0
II
CII2-C-0H
and can be accomplished by following one of the 50 several procedures known in the art for the demethylation of aryl methyl ethers. One such procedure, described by Feutrill et a\.,Aust. J. Chem., 25, 1719 (1972), involves tffe treatment of the aryl methyl ether with thioethoxide ion 55 (readily prepared in situ from ethanethiol and sodium hydride) in a polar aprotic solvent, preferably dimethylformamide.
The phenolic hydroxy group of a compound of formula VI can be protected with an alkanoyl 60 group using art-recognized procedures. One such procedure comprises reacting the glutaric acid derivative with the appropriate acid anhydride (acetic anhydride is preferred). The preferred method of preparing a glutaric anhydride 05 derivative of formula I from the glutaric acid derivative of formula VI is to combine the conversion of the acid to anhydride and the protection of the phenolic hydroxy group into a single step. When the R, protecting group is 70 acetyl, this would involve heating a glutaric acid derivative of formula VI in acetic anhydride.
Example 1
3-(4-Acetyloxyphenyl)glutaric Anhydride
A) 3-(4-Methoxyphenyl)glutaric Acid
75 A mixture of p-anisaldehyde (27.2g). ethyl acetoacetate (52.1 g) and piperidine (4 ml) in 95% ethanol (10 ml) is stirred at room temperature for 5.0 hours while a solid forms. The solid is isolated by filtration, washed with 25% ethanol and 80 crystallized from 95% ethanol to afford ethyl 2,2'-(4-methoxybenzal)j&/s-aceto-acetate (31.4g), melting point 138-—141 °C. The filtrate on dilution with an equal amount of water gives a solid which is crystallized from 95% ethanol to 85 afford another crop of material (8.5g), melting point 137—142°C.
A mixture of ethyl 2,2'-(4-methoxybenzal(-/fr/'s-acetoacetate (30g), ethanol (450 ml) and 50% sodium hydroxide (450g) is refluxed vigorously for 90 1.0 hour. Water (1 50 ml) is added and most of the ethanol is removed by distillation in vauo. The concentrate is acidified with concentrated hydrochloric acid and is extracted with ethyl acetate. The ethyl acetate solution is washed with 95 brine, dried, evaporated, and the residue is crystallized from benzene-methanol to afford 3.3g of 3-(4-methoxyphenyl)glutaric acid, melting point 147—150°C.
B) 3-(4-Hydroxyphenyl)glutaric Acid
100 To a stirred suspension of 57% sodium hydride-paraffin (6.45g), in dry
2
GB 2 027 425 A 2
dimethylformamide (70 ml) is slowly added ethanethiol (11.89 ml) in dry dimethylformamide (20 ml). After stirring the resultant slurry for 15 minutes, a solution of 3-(4-5 methoxyphenyOglutaric acfd (3.0g) in dry dimethylformamide (20 ml) is added. The slurry is heated in a bath at 165°C for 5.0 hours and most of the solvent is removed by distillation in vaco. The residue is diluted with water, acidified with 10 concentrated hydrochloric acid and extracted twice with ether (the extracts are discarded). The solution is saturated with sodium chloride and extracted with ethyl acetate. The ethyl acetate solution is washed once with brine, dried and the 15 residue crystallized from chloroform-hexane to afford 2.3g of 3-(4-hydroxyphenyl)-glutaric acid, melting point 168—170°C.
C) 3-(4-Acetyloxyphenyl)glutaric Anhydride
A solution of 3-(4-Hydroxyphenyl)glutaric acid 20 (800 mg) in acetic anhydride (15 ml) is heated at 100°C for 2.5 hours and evaporated to dryness in vacuo. The residual solid is crystallized from chloroform-hexane to afford 600 mg of 3-(4-acetyloxyphenyDglutaric anhydride, melting point 25 140—143°C.
Example 2
3-[[(4-Acetyloxy)phenyl]methyl]glutaric Anydride
A) 3-[(4-Methoxyphenyl)methyl]glutaric Acid
30 To a solution of cyanoacetic acid (3.57g), in water 20 ml is added a solution of sodium hydroxide (2.08g) in water (20 ml). The solution is diluted with glyme (70 ml)., 4-methyoxyphenyl acetaldehyde (3.0g) is added and the mixture is 35 left at room temperature for 6.0 hours. The glyme is evaporated in vacuo, and the residue is mixed with 10% hydrochloric acid (200 ml) and refluxed for 6.0 hours. After cooling, the mixture is extracted with ethyl acetate. The ethyl acetate 40 extract is washed once with brine, dried, evaporated and the residue subjected to chromoatography on a column of silica gel using chloroform-ethyl acetate mixtures for elution to afford 2.2g of 3-[(4-methoxyphenyl) 45 methyljglutaric acid. Crystallization from a benzene-ethyl acetate-hexane mixture gives a specimen having a melting point 109—110°C.
B) 3-[(4-Hydroxyphenyl)methyl]glutaric Acid
To a stirred suspension of 57% sodium 50 hydride-paraffin (1.4g) in dry dimethylformamide (30 ml) is added dropwise a solution of ethanethiol (4.0 ml) in dry dimethylformamide (10 ml). After 15 minutes, a solution of 3-[(4-methoxyphenyl)methyl]glutaric acid (800 mg) in 55 dry dimethylformamide (20 ml) is added. The resulting slurry is heated in a bath at 165°C for 20 hours and evaporated in vacuo. The residue is acidified with 20% hydrochloric acid, extracted with ether and the extracts are discarded. The 60 aqueous solution is saturated with salt and extracted with ethyl acetate. The extracts are combined, washed once with brine, dried,
evaporated and the residue crystallized from a mixture ofethyl acetate-chloroformhexane to give 65 600 mg of 3-[(4hydroxyphenyl) methyljglutaric acid, melting point 117—119°C.
C) 3-[[(4-Acetyloxy)phenyI]methyl]glutaric Anhydride
3-[(4Hydroxyphenyl)methyl]glutaric acid (500 70 mg) in acetic anhydride (15 ml) is heated in a bath at 120°C for 2 hours. The solution is then evaporated to dryness in vacuo and the residue « triturated with chloroform-hexane to afford 490 mg of the title compound, melting point 88— 75 89°C.
Example 3
3-[2-[4-AcetyIoxy) Phenyl]ethyl]gIutaric Anhydride
A) 3-[2-{4-Methoxyphenyl)ethyl]glutaric 80 Acid
To a solution of cyanoacetic acid (850 mg) in water (5.0 ml) is added a solution of sodium hydroxide (440 mg) in water (10 ml). The solution is diluted with glyme (15 ml) and 3-(4-85 methoxyphenyl)propionaldehyde (820 mg) is added. The solution is kept at room temperature for 10 hours and then evaporated to remove the glyme. To the residue is added 10% hydrochloric acid (50 ml) and the mixture is thereafter refluxed 90 for 6 hours with stirring. It is then cooled and extracted with ethyl acetate. The extract is washed with brine, dried over anhydrous magnesium sulfate and evaporated. The residue is subjected to chromotography over silica gel (15 95 g) to isolate in chloroform-ethyl acetate (80/20) fraction, 600 mg of the title compound. Crystallization from ethyl acetatebenzene gives a specimen having a melting point of 98—100°C.
B) 3-[2-(4-Hydroxyphenyl)ethyl]glutaric Acid
100 To a suspension of 57% sodium hydride-
paraffin (2.2g) in dry dimethylformamide (70 ml) in an atmosphere of nitrogen is slowly added ethanethiol (4.0 ml). The mixture is stirred at room temperature until a clear solution results. To 105 this solution is added a solution of 3-[2-(4-
methoxyphenyl) ethyl-glutaric acid (1.2 g) in dry dimethylformamide (10 ml) and the mixture is heated with stirring in a bath at 165°C for 6.0 hours. The mixture is then evaporated to dryness 110 in vacuo and the resulting residue is dissolved in water (50 ml), extracted with ether (two 50 ml portions) and the ether extract is discarded. The aqueous solution is acidified with concentrated hydrochloric acid and extracted with ethyl 115 acetate. The ethyl acetate solution is washed with brine, dried with anhydrous magnesium sulfate, and evaporated to a residue. Crystallization of this from chloroform-hexane affords 1 .Og of the title compound, melting point 142-144°C.
120 C) 3-[2-]4-Acetyloxy)phenyl]ethyl]glutaric Anydride
A solution of 3-[2-(4-hydroxyphenyl)ethyl]glutaric acid (600 mg) in
GB 2 027 425 A
acetic anhydride (15 ml) is heated in a bath at 120°C for 2.0 hours. It is evaporated in vacuo and the residue is crystallized from dichloromethane-hexane to afford 495 mg of 3-[2-[4-5 (acetyloxy)phenyl]-ethyl]-giutaric anhydride, melting point 97—99°C.
Example 4
3-[3-[4-(Acetyloxy)phenyl]propyl]glutaric Anhydride
10 A) 3-[3-(4-Methoxyphenyl)propyl]glutaric Acid
4-(4-Methoxyphenyl)butyraldehyde (5.34 g) is reacted with cyanoacetic acid (5.15 g) and sodium hydroxide (2.74 g) in a mixture of glyme 15 (50 ml) and water (60 ml). The mixture is treated with hydrochloric acid and processed as described in Example 2A to afford the title compound (2.1 g) which on crystallization from ethyl acetate-chloroform-hexane had a melting 20 point of 71—73°C.
B) 3-[3-4-(Hydroxyphenyl)propyl]glutaric Acid
3-[3-(4-Methoxyphenyl)propyl]glutaric acid (2.0g) is demethylated by the procedure 25 described in Example 1B to afford, after crystallization of the product from ethyl acetate-chloroform-hexane, 1.2 g of 3-[3-(4-hydroxyphenyl)-propyl]glutaric acid, melting point 107—108°C.
30 C) 3-[3-[4-(Acetyloxy)phenyl]propyl]g!utaric Anhydride
3-[3-(4-Hydroxyphenyl)propyl]glutaric acid (533 mg) is reacted with acetic anydride as described in Example 1C to afford 3-[3-[4-35 (acetyloxy)phenyl]propyl]glutaric anhydride, melting poing 55—57°C.
Example 5
3-[4-[4-(Acetyloxy)phenyI]butyl]glutaric Anhydride
40 Following the procedure of Example 4, but substituting 5-(4-methoxyphenyl)valeraldehyde for 4(4-methoxyphenyl)-butyraldehyde yields the title compound.
and extracted with ethyl acetate to afford the title compound.
B) 3-(4-Hydroxy-3-methylphenyl)glutaric 60 Acid
Following the procedure described in Example
IB, but substituting 3-(4-methoxy-3-methylphenyDglutaric acid for 3-(4-methoxyphenyDglutaric acid, yields the title
65 compound.
C) 3-[4-(Acetyloxy)-3-methylphenyl)]glutaric Anhydride
Following the procedure described in Example
IC, but substituting 3-(4-hydroxy-3-70 methylphenyDglutaric acid for 3-(4-
hydroxyphenyDglutaric acid, yields the title compound.

Claims (10)

Claims
1. A compound having the formula
.OBj—0 ^
75 Hi-°—/ V-C^n «
•cHjr
wherein R is hydrogen or an alkyl group having 1 to 3 carbon atoms; R, is alkanoyl having 2 to 6 carbon atoms and n is 0,1,2,3 or 4.
2. A compound in accordance with claim 1 80 wherein R, is acetyl and R is hydrogen.
3. A compound in accordance with claim 1 or 2 wherein n is 0.
4. A compound in accordance with claim 1 or 2 wherein n is 1.
85
5. A compound in accordance with claim 1 or 2 wherein n is 2.
6. A compound in accordance with claim 1 or 2 wherein n is 3.
7. A compound in accordance with claim 1 or 2 90 wherein n is 4.
8. A compound having the formula
CH^O
0
pv
JH
Example 6
45 3-[4-(Acetyloxy)-3-methylphenyl)]glutaric Anhydride
A) 3-(4-Methoxy-3-methylphenyl)glutaric Acid
A mixture of 4-methoxy-3-50 methylbenzaldehyde (100 mmole), cyanoacetic acid (210 mmole) and potassium hydroxide (250 mmole) (in water 500 ml) is stirred at room temperature for 20 hours. The resulting solution is acidified with concentrated hydrochloric acid 55 (100 ml) and the mixture is refluxed for 60 hours. After cooling, it is saturated with sodium chloride
95
wherein R is hydrogen or an alkyl group having 1 to 3 carbon atoms and n is 1,2, 3 or 4.
9. A compound having the formula
J/ \ (CH.) —fH
cii2-c-oh
Z'n wherein R is hydrogen or alkyl having 1 to 3 carbon atoms and n is 1, 2, 3 or 4.
10. A compound in accordance with Claim 1, 8 100 or 9 as named in any of the Examples.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.
GB7921396A 1977-08-12 1978-08-14 Glutaric acid and anhydride dervatives Expired GB2027425B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US82401677A 1977-08-12 1977-08-12
US05/901,952 US4230621A (en) 1978-05-01 1978-05-01 Steroid derivatives and their use in radioimmunoassays

Publications (2)

Publication Number Publication Date
GB2027425A true GB2027425A (en) 1980-02-20
GB2027425B GB2027425B (en) 1982-03-03

Family

ID=27124779

Family Applications (2)

Application Number Title Priority Date Filing Date
GB7833217A Expired GB2002385B (en) 1977-08-12 1978-08-14 Steroid derivatives and their use in radioimmunoassays
GB7921396A Expired GB2027425B (en) 1977-08-12 1978-08-14 Glutaric acid and anhydride dervatives

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GB7833217A Expired GB2002385B (en) 1977-08-12 1978-08-14 Steroid derivatives and their use in radioimmunoassays

Country Status (7)

Country Link
JP (1) JPS5436247A (en)
CA (1) CA1118409A (en)
DE (1) DE2834516A1 (en)
FR (1) FR2400035A1 (en)
GB (2) GB2002385B (en)
IT (1) IT7850710A0 (en)
NL (1) NL7808393A (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4323511A (en) * 1978-05-22 1982-04-06 E. R. Squibb & Sons, Inc. Steroid derivatives and their use in radioimmunoassays
US4209614A (en) * 1978-05-30 1980-06-24 E. R. Squibb & Sons, Inc. Vitamin B12 derivative suitable for radiolabeling
US4243608A (en) * 1979-05-14 1981-01-06 E. R. Squibb & Sons, Inc. 3-(4-Hydroxyphenyl)pentanedioic acid, monohydrazide, derivatives and analogs
US4366143A (en) * 1979-09-24 1982-12-28 Amersham International Public Limited Company Assay for the free portion of substances in biological fluids
JPS58194900A (en) * 1982-05-10 1983-11-12 Shionogi & Co Ltd 4- or 6-substituted aldosterones, its preparation and method for using the same in immunoassay
JPS59228097A (en) * 1983-06-07 1984-12-21 横河電機株式会社 Paper thickness profile control apparatus
JPS61108794A (en) * 1984-08-08 1986-05-27 インパクト　システムズ　インコ−ポレ−テツド Thickness control apparatus and method
JP2015193545A (en) * 2014-03-31 2015-11-05 国立大学法人京都大学 2-(3-pyridinyl)-1h-benzimidazole derivative compound, and radioactive pharmaceuticals containing the same

Also Published As

Publication number Publication date
GB2027425B (en) 1982-03-03
FR2400035B1 (en) 1981-02-13
GB2002385B (en) 1982-02-24
DE2834516A1 (en) 1979-02-22
CA1118409A (en) 1982-02-16
GB2002385A (en) 1979-02-21
IT7850710A0 (en) 1978-08-11
FR2400035A1 (en) 1979-03-09
JPS5436247A (en) 1979-03-16
NL7808393A (en) 1979-02-14

Similar Documents

Publication Publication Date Title
EP0092136B1 (en) Benzoquinone derivatives and production thereof
US20070293690A1 (en) Process for Production of Azulene Derivatives and Intermediates for the Synthesis of the Same
EP2202215B1 (en) Novel process for the synthesis of (E)-Stilbene derivatives which makes it possible to obtain resveratrol and piceatannol
JP3202607B2 (en) Method for producing 2- (4-alkoxy-3-cyanophenyl) thiazole derivative
JP2012528114A (en) Method for producing benzofuran
US4425273A (en) Process for production of chenodeoxycholic acid
GB2027425A (en) Glutaric Acid and Anhydride Derivatives
JPS632247B2 (en)
EP0089711B1 (en) Process for preparing esters of 2-(6&#39;-methoxy-2&#39;-naphthyl)-propionic acid
CA1211455A (en) Method of producing quinone derivatives
EP0690835B1 (en) Formylation process for aromatic aldehydes
EP0271275B1 (en) Trifluorohydroxyaromatic acid and preparation thereof
EP0490063B1 (en) Process for the preparation of insecticidal, acaricidal and molluscicidal 2-halopyrrole-3-carbonitrile compounds
JP2826646B2 (en) 3-substituted-5-halogenopyridine derivatives
US4182880A (en) 1,8-Naphthyridine compounds and process for preparing the same
HU194154B (en) Process for producing esters of 4-/acyloxy/-3-oxo-butiric acid
EP0015631B1 (en) ((4,5-dihydro-5-thioxo-1h-1,2,4-triazol-3-yl)thio)acetic acid and its salts
US4201870A (en) Process for the preparation of 2-(3-benzoylphenyl)-propionic acid
US4908470A (en) Process for the methyl-4-(dimethylamino)-3,5-dimethoxybenzoate
JPH05148175A (en) Production of p-dimethoxybenzene derivative
Nakatani et al. Total Synthesis of (±)-Sermundone and An Alternative Cyclization Method to Dehydrorotenoids
Dimsdale The formation of 2‐alkoxyquinolines from quinoline N‐oxides in alcoholic media
JPH06279414A (en) Preparation of aryl hydantoin
JPH0420904B2 (en)
US3057876A (en) Process for making 2-(6-hydroxy-2-methoxy-3, 4-methylenedioxyphenyl)benzofuran

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee