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SU482039A3 - Method for preparing biphenylyl butenoic acids or their derivatives - Google Patents

Method for preparing biphenylyl butenoic acids or their derivatives

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Publication number
SU482039A3
SU482039A3 SU1958291A SU1958291A SU482039A3 SU 482039 A3 SU482039 A3 SU 482039A3 SU 1958291 A SU1958291 A SU 1958291A SU 1958291 A SU1958291 A SU 1958291A SU 482039 A3 SU482039 A3 SU 482039A3
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biphenylyl
derivatives
preparing
acid
acids
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SU1958291A
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Russian (ru)
Inventor
Энгель Вольфхард
Тойфель Гельмут
Зеегер Эрнст
Никл Иозеф
Энгельхардт Гюнтер
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Д-Р Карл Томэ Гмбх (Фирма)
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    • C07C245/12Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
    • C07C245/14Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom having diazo groups bound to acyclic carbon atoms of a carbon skeleton
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C07C17/202Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
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    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
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Description

(54) СПОСОБ ПОЛУЧЕНИЯ БИФЕНИЛИЛБУТЕНОВЫХ КИСЛОТ. ИЛИ ИХ ПРОИЗВОДНЫХ(54) METHOD FOR OBTAINING BIPHENYLYLBUTENE ACIDS. OR THEIR DERIVATIVES

которые обладают более высокой биопоги ческой активностью, чем известнее соедннени  того же назначени , например фе- нилбутазон.which have a higher biopogic activity than the known compounds of the same purpose, for example phenylbutazone.

Способ заключаетс  в том, что Д -ок сикислоты или их производные общей формулыThe method consists in the fact that the D-hydroxy acids or their derivatives of the general formula

«1"one

(и) он (and he

где I и в имеют указанные значени ,where I and in have the indicated values,

дегидратируют с помощью водоотнимак щегос  средства в среде инертного растворител , несмешивающегос  с водой, при нагревании не выще температуры кипени  реакционной смеси с последующим выделением целевого продукта и/или переводом его в кислоту, соль, амид или сложный эфир известными способами .dehydrated with water-withdrawing means in an inert solvent immiscible with water, when heated, not more than the boiling point of the reaction mixture, followed by isolation of the target product and / or its conversion into acid, salt, amide or ester by known methods.

В качестве водоотщепл ющего средства целесообразно примен ть соли П1фидина или алкилпиридинов с галогеноводороднымц кислотами, бисульфат кали , соли металлов такие как хлорид цинка, а также кислоты, например П--толуолсульфокислоту, фосфорную , серную кислоту, или, если В означает алкоксигруппу, то преимущественно галоидангидриды неорганических кислот, например хлорокись фосфора. В качестве инертного растворител  примен ют преимущественно бензол, толуол или ксилол.Salt of P1fidine or alkylpyridines with hydrohalic acids, potassium bisulfate, metal salts such as zinc chloride, as well as acids, for example, P-toluenesulfonic acid, phosphoric, sulfuric acid, or, if B means an alkoxy group, preferably inorganic acid halides, for example phosphorus oxychloride. Preferably, benzene, toluene or xylene is used as the inert solvent.

Следует указать, что при получении смеси соединений общей формулы , в которой А означает группу СНзIt should be noted that when preparing a mixture of compounds of the general formula, in which A represents a CH3 group

СН2 CH2

СН2-,CH2-,

эту смесь можно разделить на отдельные компоненты хроматографически или фракционной кристаллизацией.This mixture can be divided into individual components by chromatographic or fractional crystallization.

В качестве органических оснований дл получени  солей кислот общей формулы используют, в частности, диэтаноламин, морфолин, циклогексиламин и пиперазин.Diethanolamine, morpholine, cyclohexylamine and piperazine are used as organic bases for the preparation of salts of acids of the general formula.

При получении соединени  общей формулы I, в которой В - радикал.Upon receipt of the compound of general formula I in which B is a radical.

.Rj H-N .Rj H-N

изсложный эфир общей формулы J, в которой В - алкоксигруп а, подвергают вза4ester of general formula J, in which B is an alkoxy group, is subjected to mutual

имодействию с первичным или вторичным амщом. Взаимодействие провод т в инерт -: ном растворителе, предпочтительно в спирте , при повыщенных температуре и давле- НИИ. Амиды кислот общей формулы I можно получать также из соединений этой формулы, в которой В - атом галогена, т. е. из галогенангидрида кислоты, и соответствующего амина формулы and action with primary or secondary amschom. The reaction is carried out in an inert solvent, preferably in an alcohol, at elevated temperature and pressure. Amides of acids of general formula I can also be obtained from compounds of this formula, in which B is a halogen atom, i.e., from an acid halide, and the corresponding amine of formula

RSRS

Пример. 3-(2 -фтор-4-бифе нилил)-2-бутенова  кислота. 4,5 г (0,015 мол ) этилового эфира 3-(2-фтор-4-бифенилил )-3-окси-масл ной кислоты (т, пл.Example. 3- (2-fluoro-4-bife nylyl) -2-butenoic acid. 4.5 g (0.015 mol) of 3- (2-fluoro-4-biphenylyl) -3-hydroxy-butyric acid ethyl ester (t, pl.

|71-73°С) раствор ют в 75 мл бензола и вместе с 3,5 г (0,0225 мол ) хлорркиси фосфора в течение 10 мин нагревают с обратным холодильником. Затем растворитель упаривают в вакууме, к остатку добавл ют лед ную воду, экстрагируют простым эфиром и отгон ют растворитель . Кристаллический остаток перекристал лизовывают из петролейного эфира. / Полученный этиловый эфир 3-(2 -фтор-4-бифенилил )-2-бутеновой кислоты (согласно ЯМР-спектру представл ет собой транс-форму) имеет т. пл. 53°С. Выход продукта 4,1 г (96% от теории).| 71-73 ° C) is dissolved in 75 ml of benzene and heated with reflux together with 3.5 g (0.0225 mol) of phosphorus chlorine for 10 minutes. The solvent is then evaporated in vacuo, ice water is added to the residue, it is extracted with ether and the solvent is distilled off. The crystalline residue is recrystallized from petroleum ether. The 3- (2-fluoro-4-biphenylyl) -2-butenoic acid ethyl ester obtained (according to the NMR spectrum is in the trans form) is m.p. 53 ° C. The product yield of 4.1 g (96% of theory).

Ч Раствор 4,1 г этилового эфира 3-( 2-фторбифен и лил)-2-бутеновой кислоты в 50 мл метанола с 1О мл, ЗО%-ного едкого кали нагревают с обратным холодильником в течение 2 час. Отгон ют метанол, добавл ют 200 мл воды и подкисл ют 15%-ной сол нс1 кислотой. Образовавщийс  осадок экстрагируют простым эфиром. После сушки над Сульфатом натри  упаривают простой эфир и остаток перекристаллизовывают из уксусного эфира. H A solution of 4.1 g of ethyl 3- (2-fluorobifen and lil) -2-butenoic acid in 50 ml of methanol with 10 ml of ZO% sodium hydroxide is heated under reflux for 2 hours. The methanol is distilled off, 200 ml of water is added and acidified with 15% hydrochloric acid. The resulting precipitate is extracted with ether. After drying over sodium sulfate, the ether is evaporated and the residue is recrystallized from ethyl acetate.

Получают 2,8 г (76% от теории) 3- (2 -фтор-4-бифенилцл)-2-бутеновой кислоты с т. пл. 177-1780С.2.8 g (76% of theory) of 3- (2-fluoro-4-biphenyl) -2-butenoic acid with m.p. 177-1780С.

Осажденна  в ацетоне соль циклогексиламина имеет т. пл. 194-195°С.The cyclohexylamine salt precipitated in acetone has an mp. 194-195 ° C.

П р и м е р 2, 3-(2 -фтор-4-бифенилил )-2-бутенова  кислота. 15 г (0,0547 мол )3-(2 -фтор-4-бифенилил)-3-окси-Macл ной Кислоты (т.пл. 108-ИО С) в 150м.| толуола с 1 г ft -толуолсульфокислоты при перемещивании нагревают с обратным холодильником и водоотделителем в течение часа. После охлаждени  добавл йэт 1ОО мл уксусного эфира, промывают органический раствор водой и упаривают растворитель. Остаток перекристаллизовывают из уксусного эфира.PRI me R 2, 3- (2-fluoro-4-biphenylyl) -2-butenoic acid. 15 g (0.0547 mol) of 3- (2-fluoro-4-biphenylyl) -3-hydroxy-Acid Acid (mp. 108-IO C) at 150 m. | toluene with 1 g of ft-toluene sulfonic acid is heated under reflux and water separator during transfer for one hour. After cooling, it is added with 1 ml of ethyl acetate, the organic solution is washed with water and the solvent is evaporated. The residue is recrystallized from ethyl acetate.

Получают 8 г 3-(2 -фтор-4-бифенилил)-2-бутеновой кислоты с т, tin, 177-178 0.8 g of 3- (2-fluoro-4-biphenylyl) -2-butenoic acid are obtained with m, tin, 177-178 0.

SU1958291A 1972-08-17 1973-08-15 Method for preparing biphenylyl butenoic acids or their derivatives SU482039A3 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2240441A DE2240441A1 (en) 1972-08-17 1972-08-17 NEW BIPHENYL DERIVATIVES AND METHOD OF MANUFACTURING

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SU482039A3 true SU482039A3 (en) 1975-08-25

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ID=5853790

Family Applications (11)

Application Number Title Priority Date Filing Date
SU1958290A SU511846A3 (en) 1972-08-17 1973-08-15 The method of obtaining -biphenylbuttonic acids or their salts
SU1958291A SU482039A3 (en) 1972-08-17 1973-08-15 Method for preparing biphenylyl butenoic acids or their derivatives
SU1958288A SU484679A3 (en) 1972-08-17 1973-08-15 Method for preparing biphenyl derivatives
SU2069110A SU554810A3 (en) 1972-08-17 1974-10-21 The method of obtaining derivatives of biphenyl or their salts, or racemates, or optically active antipodes
SU7402069575A SU577967A3 (en) 1972-08-17 1974-10-21 Method of preparing substituted biphenylilbutyric acid or its esters,or its amides,or its salts
SU2069771A SU520030A3 (en) 1972-08-17 1974-10-21 Method for preparing substituted biphenylbutyric acid or its ester or its salt
SU2069774A SU552021A3 (en) 1972-08-17 1974-10-21 The method of obtaining derivatives of biphenyl or their salts
SU2069114A SU538658A3 (en) 1972-08-17 1974-10-21 The method of obtaining biphenylbutyric acids or their salts, or racemates, or optically active antipodes
SU2069576A SU561505A3 (en) 1972-08-17 1974-10-21 The method of obtaining 3- (4-biphenylyl) -buttonic acid or its salts
SU2069577A SU520907A3 (en) 1972-08-17 1974-10-21 Method for preparing substituted biphenylyl butyric acid or its salt
SU2069578A SU511847A3 (en) 1972-08-17 1974-10-21 Method for preparing substituted biphenylbutyric acid or its esters or salts

Family Applications Before (1)

Application Number Title Priority Date Filing Date
SU1958290A SU511846A3 (en) 1972-08-17 1973-08-15 The method of obtaining -biphenylbuttonic acids or their salts

Family Applications After (9)

Application Number Title Priority Date Filing Date
SU1958288A SU484679A3 (en) 1972-08-17 1973-08-15 Method for preparing biphenyl derivatives
SU2069110A SU554810A3 (en) 1972-08-17 1974-10-21 The method of obtaining derivatives of biphenyl or their salts, or racemates, or optically active antipodes
SU7402069575A SU577967A3 (en) 1972-08-17 1974-10-21 Method of preparing substituted biphenylilbutyric acid or its esters,or its amides,or its salts
SU2069771A SU520030A3 (en) 1972-08-17 1974-10-21 Method for preparing substituted biphenylbutyric acid or its ester or its salt
SU2069774A SU552021A3 (en) 1972-08-17 1974-10-21 The method of obtaining derivatives of biphenyl or their salts
SU2069114A SU538658A3 (en) 1972-08-17 1974-10-21 The method of obtaining biphenylbutyric acids or their salts, or racemates, or optically active antipodes
SU2069576A SU561505A3 (en) 1972-08-17 1974-10-21 The method of obtaining 3- (4-biphenylyl) -buttonic acid or its salts
SU2069577A SU520907A3 (en) 1972-08-17 1974-10-21 Method for preparing substituted biphenylyl butyric acid or its salt
SU2069578A SU511847A3 (en) 1972-08-17 1974-10-21 Method for preparing substituted biphenylbutyric acid or its esters or salts

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JP (2) JPS49124052A (en)
AT (3) AT328427B (en)
AU (2) AU476340B2 (en)
BE (3) BE803734A (en)
BG (3) BG21844A3 (en)
CH (1) CH588435A5 (en)
CS (3) CS165386B2 (en)
DD (2) DD108071A5 (en)
DE (1) DE2240441A1 (en)
ES (4) ES417883A1 (en)
FR (2) FR2196167B1 (en)
GB (2) GB1411495A (en)
HU (2) HU166517B (en)
IL (2) IL43004A0 (en)
NL (2) NL7311301A (en)
PL (2) PL94510B1 (en)
RO (2) RO62918A (en)
SU (11) SU511846A3 (en)
ZA (3) ZA735629B (en)

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Publication number Priority date Publication date Assignee Title
FR2457275A1 (en) * 1979-05-21 1980-12-19 Fabre Sa Pierre P-BIPHENYL-4 METHYL-2 BUTEN-3 OIC ACIDS USEFUL IN THE TREATMENT OF RHUMATISMS
RU2686489C1 (en) * 2018-12-27 2019-04-29 Федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский государственный университет (СПбГУ)" Method of producing α-diazocarbonyl compounds in aqueous medium

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GB1382267A (en) * 1970-05-05 1975-01-29 Rorer Inc William H Phenylalkanoic acid derivatives
BE776316R (en) * 1971-03-10 1972-06-06 Rorer Inc William H Phenylacetic acid derivs - as antiinflammatory agents

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FR2196168B1 (en) 1977-02-25
ZA735616B (en) 1976-01-28
ZA735629B (en) 1976-01-28
SU484679A3 (en) 1975-09-15
NL7311300A (en) 1974-02-19
SU577967A3 (en) 1977-10-25
NL7311301A (en) 1974-02-19
SU520907A3 (en) 1976-07-05
SU511847A3 (en) 1976-04-25
BE803732A (en) 1974-02-18
CS165387B2 (en) 1975-12-22
BG21197A3 (en) 1976-03-20
IL43004A0 (en) 1973-11-28
AU5930873A (en) 1975-02-20
CH588435A5 (en) 1977-05-31
CS165386B2 (en) 1975-12-22
FR2196168A1 (en) 1974-03-15
SU538658A3 (en) 1976-12-05
DD107901A5 (en) 1974-08-20
ATA711273A (en) 1975-06-15
SU552021A3 (en) 1977-03-25
BE803734A (en) 1974-02-18
ES432465A1 (en) 1976-11-16
ZA735628B (en) 1975-04-30
AT323144B (en) 1975-06-25
SU520030A3 (en) 1976-06-30
ES432464A1 (en) 1977-02-16
FR2196167B1 (en) 1977-04-15
GB1410852A (en) 1975-10-22
RO62917A (en) 1978-02-15
PL94510B1 (en) 1977-08-31
SU511846A3 (en) 1976-04-25
JPS49124051A (en) 1974-11-27
HU166516B (en) 1975-03-28
FR2196167A1 (en) 1974-03-15
PL90397B1 (en) 1977-01-31
AT323143B (en) 1975-06-25
AU5930973A (en) 1975-02-20
BG21844A3 (en) 1976-09-20
JPS49124052A (en) 1974-11-27
DE2240441A1 (en) 1974-02-28
BG22069A3 (en) 1976-11-25
IL43003A0 (en) 1973-11-28
SU554810A3 (en) 1977-04-15
HU166517B (en) 1975-03-28
AT328427B (en) 1976-03-25
DD108071A5 (en) 1974-09-05
CS165385B2 (en) 1975-12-22
GB1411495A (en) 1975-10-29
ES417884A1 (en) 1976-03-16
BE803733A (en) 1974-02-18
RO62918A (en) 1978-04-15
AU476340B2 (en) 1976-09-16
SU561505A3 (en) 1977-06-05
ES417883A1 (en) 1976-11-16

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