SU600138A1 - Method of preparing oxy-derivatives of 2-arylbenzasols - Google Patents
Method of preparing oxy-derivatives of 2-arylbenzasolsInfo
- Publication number
- SU600138A1 SU600138A1 SU762379997A SU2379997A SU600138A1 SU 600138 A1 SU600138 A1 SU 600138A1 SU 762379997 A SU762379997 A SU 762379997A SU 2379997 A SU2379997 A SU 2379997A SU 600138 A1 SU600138 A1 SU 600138A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- solution
- derivatives
- arylbenzasols
- phosphoric acid
- benzimidazole
- Prior art date
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
eoci ж,eoci well
11 41 :i-11 41: i-
NO,NO,
ОСИOSI
)НСО ) NSO
ОСНзOSSN
Pd N0, Pd N0,
-ННСО-Ч VOCH3-NNO-H VOCH3
V- /НС1V- / HC1
Н,СО H, CO
н,соn co
7JH,7JH,
оснDOS
/ НВр48°/о/ HBr48 ° / o
Несмотр на р д преимуществ (высока чистота конечного продукта, нес-чожное аппаратурное оформление), этот метод вл етс многостадийным, в результате чего общий выход невысок (55%), хот на всех стади х выходы составл ют не менее 90%. Другим не менее важным недостатком вл етс использование агрессивных веществ и сред (хлорангидриды , бромистоводородна и сол на кислоты ).Despite a number of advantages (high purity of the final product, incomplete instrumentation), this method is multistage, resulting in a low overall yield (55%), although at all stages the yields are at least 90%. Another equally important drawback is the use of aggressive substances and media (acid chlorides, hydrobromic acid and hydrochloric acid).
Цель изобретени - разработка удобного в препаративном отношении способа получени оксипроизводных 2-арилбензазола, позвол ющего повысить выход целевого продукта.The purpose of the invention is the development of a preparative method for the preparation of the hydroxy derivatives of 2-arylbenzazole, which makes it possible to increase the yield of the target product.
Достигаетс это предлагаемым способом получени соедипений общей формулы 1, заключающимс в том, что соединение общей формулыThis is achieved by the proposed method of obtaining compounds of general formula 1, which consists in the fact that the compound of general formula
где R2 - водород, окси или аминогр шпа,where R2 is hydrogen, hydroxy or aminogr shpa
X и Y имеют указанные значени и Ri - водород или аминогруппа, диазотируют в 45-55%-ной о-фосфорной кислоте при температуре от О до +5°С с последующим добавлением полученной смеси к предварительно нагретой до кнпени концентрированной о-фосфорной кислоте.X and Y have the indicated values and Ri is hydrogen or an amino group, is diazotized in 45-55% o-phosphoric acid at a temperature from 0 to + 5 ° C, followed by addition of the resulting mixture to the preheated to phosphoric acid concentrated o-phosphoric acid.
Реакцию диазотировани провод т в 45- 55%-ной о-фосфорной кислоте при О-5°С. Полученное диазосоединение в виде суспензии добавл ют без выделени к нагретой до кипени 85%-ной о-фосфорпой кислоте. Разложение диазосоединени в этих услови х протекает очень легко, так что на его добавление необходимо не более 1-2 ч. Контроль за ходом реакции ведетс по исчезновению реакции азосочетани пробы реакционного раствора со щелочным раствором |3-нафтола. К концу реакции все переходит в раствор. Выделение целевого дноксипроизводного проводитс нейтрализацией реакционного раствора 10-20%-ным раствором едкого натра при охлаждении.The diazotization reaction is carried out in 45-55% o-phosphoric acid at-5 ° C. The resulting diazo compound as a suspension is added without isolation to the 85% o-phosphoric acid heated to boiling. The decomposition of the diazo compound under these conditions proceeds very easily, so that its addition requires no more than 1–2 hours. The reaction progress is monitored by the disappearance of the azo-coupling reaction of the sample of the reaction solution with an alkaline solution of 3-naphthol. By the end of the reaction, everything goes into solution. The selection of the desired dinoxy derivative is carried out by neutralizing the reaction solution with a 10-20% sodium hydroxide solution while cooling.
Предлагаемый способ позвол ет получать целевой продукт в две стадии с общим выходом 90-95%, счита на исходный диамин.The proposed method allows to obtain the desired product in two stages with a total yield of 90-95%, based on the starting diamine.
Кроме того, в р де случаев синтез целевого продукта осуществл ют из вынускаемого промышленностью диамина.In addition, in a number of cases, the synthesis of the target product is carried out from a commercially available diamine.
Пример 1. 5(6)-Окси-2-(п-оксифенил)бензимидазол .Example 1. 5 (6) -Oxy-2- (p-hydroxyphenyl) benzimidazole.
0,02 моль 5(6)-амино-2-(«-аминофенил)бензимидазола раствор ют в 100 мл 50%-ной о-фосфорной кислоты, раствор охлаждают до О-5°С и при интенсивном перемешивании добавл ют под слой жидкости 0,04 моль нитрита натри в виде 25%-ного раствора до по влени его устойчивого избытка по иодокрахмальной бумаге. По окончании добавлени нитрита натри раствор выдерживают при О-5°С в течение 1 ч. По окончании выдержки нолученный раствор добавл ют небольшими порци ми к предварительно нагретому до кипени раствору 85%-ной о-фосфорной кислоты (100 мл). КаждуЕо следующую порцию ввод т только после прекращени азосочетани пробы реакционной массы со щелочным раствором |3-нафтола.0.02 mol of 5 (6) -amino-2 - ("- aminophenyl) benzimidazole is dissolved in 100 ml of 50% o-phosphoric acid, the solution is cooled to O-5 ° C and with vigorous stirring a liquid layer is added 0.04 mol of sodium nitrite in the form of a 25% solution before the appearance of its stable excess on starch paper. At the end of the addition of sodium nitrite, the solution is kept at about -5 ° C for 1 hour. At the end of the exposure, the resulting solution is added in small portions to a pre-heated to boiling solution of 85% o-phosphoric acid (100 ml). Each Еo the next portion is injected only after the termination of the azo-coupling of the sample of the reaction mass with the alkaline solution of | 3-naphthol.
После добавлени всего количества диазосоединени реакционную массу выдерживают при кипении 1-2 ч, охлаждают до комнатной температуры, нейтрализуют раствором соды до РН 7. Выпавший осадок 5(6)-окси-2 ( -оксифенил) -бензимидазола отфильтровывают , промывают водой, сушат.After adding the total amount of diazo compound, the reaction mass is kept at boiling for 1-2 h, cooled to room temperature, neutralized with soda solution to pH 7. The precipitated 5 (6) -oxy-2 (-oxyphenyl) -benzimidazole is filtered off, washed with water, and dried.
Выход 90-92%, т. пл. 283-285°С (из HgO), лит. т. пл. 280-285°С.The output of 90-92%, so pl. 283-285 ° С (from HgO), lit. m.p. 280-285 ° C.
Пример 2. 5(6)-Окси-2-(2-оксифенил)бензимидазол .Example 2. 5 (6) -Oxy-2- (2-hydroxyphenyl) benzimidazole.
Раствор диазосоединени в 50%-ной о-фосфорной кислоте из 0,02 моль 5(6)-амино-2-(2оксифенил )-бензимидазола подвергают разложению по примеру 1.A solution of the diazo compound in 50% o-phosphoric acid from 0.02 mol of 5 (6) -amino-2- (2-oxyphenyl) -benzimidazole is subjected to decomposition as in example 1.
Выход 89-92%, т. пл. 246-248 0.Output 89-92%, so pl. 246-248 0.
Пайдено, %: N 12,71; 12,54.Paydeno,%: N 12.71; 12.54.
CisHioNzOs. Вычислено, %: N 12,37.CisHioNzOs. Calculated,%: N 12.37.
Rf Q,9Q (элюент спирт-бензол 10:1).Rf Q, 9Q (eluent alcohol benzene 10: 1).
voH 3455cM-i (КВг).voH 3455cM-i (KVG).
Пример 3. 2-(2,4-Диоксифенил)-бензимидазол .Example 3. 2- (2,4-Dioxyphenyl) -benzimidazole.
Получен аналогично нримеру 1 из 2-(2,4диаминофенил ) -бензимидазола.Prepared similarly to example 1 from 2- (2,4-diaminophenyl) -benzimidazole.
Выход 82-90%; т. пл. 269°С.Yield 82-90%; m.p. 269 ° C.
Найдено, %: С 68,45; Н 4,55; 4,93;Found,%: C 68.45; H 4.55; 4.93;
Ci3HioN202.Ci3HioN202.
Вычислено, %: С 69,03; Н 4,43; 0,90 (элюент этанол-бензол 10 : 1). voH 3360cM-i.Calculated,%: C 69.03; H 4.43; 0.90 (eluent ethanol-benzene 10: 1). voH 3360cM-i.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU762379997A SU600138A1 (en) | 1976-06-25 | 1976-06-25 | Method of preparing oxy-derivatives of 2-arylbenzasols |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU762379997A SU600138A1 (en) | 1976-06-25 | 1976-06-25 | Method of preparing oxy-derivatives of 2-arylbenzasols |
Publications (1)
Publication Number | Publication Date |
---|---|
SU600138A1 true SU600138A1 (en) | 1978-03-30 |
Family
ID=20668333
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SU762379997A SU600138A1 (en) | 1976-06-25 | 1976-06-25 | Method of preparing oxy-derivatives of 2-arylbenzasols |
Country Status (1)
Country | Link |
---|---|
SU (1) | SU600138A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005053631A1 (en) * | 2003-12-04 | 2005-06-16 | Dsm Ip Assets B.V. | Microcapsules with uv filter activity and process for producing them |
WO2006026316A2 (en) * | 2004-08-26 | 2006-03-09 | Wyeth | Prodrug substituted benzoxazoles as estrogenic agents |
-
1976
- 1976-06-25 SU SU762379997A patent/SU600138A1/en active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005053631A1 (en) * | 2003-12-04 | 2005-06-16 | Dsm Ip Assets B.V. | Microcapsules with uv filter activity and process for producing them |
WO2006026316A2 (en) * | 2004-08-26 | 2006-03-09 | Wyeth | Prodrug substituted benzoxazoles as estrogenic agents |
WO2006026316A3 (en) * | 2004-08-26 | 2006-05-26 | Wyeth Corp | Prodrug substituted benzoxazoles as estrogenic agents |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101879468B1 (en) | Process for preparation of rilpivirine intermediate | |
SU600138A1 (en) | Method of preparing oxy-derivatives of 2-arylbenzasols | |
US4670191A (en) | Process for the preparation of N-phosphonomethylglycine | |
JPH0130826B2 (en) | ||
JPS6187651A (en) | P-formyl-n,n-dipolyoxyalkyleneaniline and manufacture | |
JPH02258768A (en) | Preparation of 5-amino-1,2,4-triazole-3-sulfonamide compound | |
EP0747449B1 (en) | Bisazo compound | |
JP3926943B2 (en) | Method for producing substituted pyridine | |
KR100377563B1 (en) | Process for preparing 2-nitro-2'-hydroxy azobenzene derivatives | |
SU436056A1 (en) | WAY OF OBTAINING 2-OXO- (OR 2-TIOXO) -4 - IMINO-5-ARYLAZOTHIAZOLIDINES; if- ^ 3 "> & ^ fi"> &? -i4; jlU: '^ a ??; C11It is proposed a method of obtaining new derivatives of 5-arylazothiazolidines, which have potential biological properties and, due to specific chemical properties, can be used for synthesis earlier hard-to-reach compounds. In the literature, the method of obtaining these compounds is not known. Only a method for producing 5-aryl-azo-andeanine or its N-substituted by the interaction of rhodanine with a diazonium salt in an organic solvent medium is known. A method for the preparation of compounds of general formula I, where R is hydrogen, phenyl, or substituted phenyl; Ar is phenyl or substituted phenyl; X is oxygen or sulfur, which means that the compound of general formula IIR-N = 1015202530, where R and X have the indicated values, is reacted with a diazonium salt of the general formula Ar-NCfII! N, where Ar has the indicated values, followed by isolation of the target compounds by known methods. The above reaction is carried out in an organic solvent medium, preferably g, of a mixture of acetic acid and anhydrous sodium acetate. Sodium 1. 5-Phenylazo-4- by them otiazoli- dong 2.0,93 g | |
Bailey et al. | Spectral compilation of dyes, intermediates, and other reaction products structurally related to FD&C Yellow No. 6 | |
Lee et al. | Intermediates in the browning reaction of triose reductone with guanine, guanosine or guanylic acid | |
RU2379283C2 (en) | Method of producing stable aryldiazonium salts | |
SU469702A1 (en) | Method for preparing 4-nitro-5-aryl-1,2,3-triazole derivatives | |
SU480700A1 (en) | Sexadentate reagents for metals1,5-di- (2-carboxymethoxyaryl) formazans | |
JPS6168479A (en) | Thiazole compound and its production | |
AU603512B2 (en) | New acrylic derivative of urea | |
SU565033A1 (en) | Monodiazotized melamin as intermadiate for obtaining ammeline | |
JPS63216861A (en) | Production of 4-hydroxyindolines | |
JPS6219426B2 (en) | ||
SU305664A1 (en) | ||
SU1432058A1 (en) | 16,17-dihydro-2,12-dinitro-5n,7n,15n-dibenzo (b,i) (1,11,4,5,7,8)-dioxatetrazacyclotetradecyne as chromogenic agent for lithium analysis, and method of producing same | |
SU1361145A1 (en) | Method of obtaining 3 (or 5)-methyl-1h-pyrazole-/5-(or 3)-azo-1ъ/-2ъ-naphthol | |
SU427013A1 (en) | METHOD OF OBTAINING 5- | |
SU952846A1 (en) | Diformazyl derivatives of dibenzo-18-crown-6 as complexones for simultaneous recovery of alkali or alkali-earth metal and transition metal, nickel, or cobalt |