SU369793A1 - - Google Patents
Info
- Publication number
- SU369793A1 SU369793A1 SU1609913A SU1609913A SU369793A1 SU 369793 A1 SU369793 A1 SU 369793A1 SU 1609913 A SU1609913 A SU 1609913A SU 1609913 A SU1609913 A SU 1609913A SU 369793 A1 SU369793 A1 SU 369793A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- methylamine
- hydrochloride
- ethylindanedione
- methylamino
- yield
- Prior art date
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 235000011167 hydrochloric acid Nutrition 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NGSZDVVHIGAMOJ-YHYXMXQVSA-N (3z)-3-propylidene-2-benzofuran-1-one Chemical compound C1=CC=C2C(=C/CC)/OC(=O)C2=C1 NGSZDVVHIGAMOJ-YHYXMXQVSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 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
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/20—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
1one
Изобретение получени замещенных индандионов , а именно гидрохлорида-2-метиламино2-этнлиндандиона-1 ,3, который может примен тьс в фармацевтической промышленности.The invention of the preparation of substituted indandions, namely hydrochloride-2-methylamino2-ethnindanedione-1, 3, which can be used in the pharmaceutical industry.
Известен способ получени гидрохлорида-2метиламино-2-этилиндандиона-1 ,3, заключающийс в том, что 2-бром-2-этилиндандион-1,3 подвергают взаимодействию с .метиламином в среде бензола, с выделением целевого продукта из реакционной среды с обработкой сол ной кислотой, с последующим осаждением основани водным аммиаком и насыщением сухим хлористым водородом.A method of producing hydrochloride-2-methylamino-2-ethyldinanedione-1, 3 is known, which consists in that 2-bromo-2-ethylindanedion-1,3 is reacted with methylamine in benzene medium to release the target product from the reaction medium with salt treatment acid, followed by precipitation of the base with aqueous ammonia and saturation with dry hydrogen chloride.
Выход целевого продукта очень низкий (7,5%).The yield of the target product is very low (7.5%).
Предлагаемый способ получени гидрохлорида-2-метиламино-2-этилиндандиона-1 ,3 заключаетс в том, что 2-бром-2-этилиндандион1 ,3 подвергают взаимодействию с метиламином в среде бензола с добавкой апротонного пол рного растворител , предпочтительно диметилформамида или диметилсульфоксида, с выделением целевого продукта из реакционной среды экстракцией 3-15% сол ной кислоты , с последующим осаждением основани 2-метиламино-2-этилиндандиона-1,3 водным аммиаком и превращением в гидрохлорид известным снособом. Выход целевого продукта 16%.The proposed method for the preparation of hydrochloride-2-methylamino-2-ethyldinanedione-1, 3 is that 2-bromo-2-ethylindanedion1, 3 is reacted with methylamine in benzene with the addition of an aprotic polar solvent, preferably dimethylformamide or dimethyl sulfoxide, with isolating the target product from the reaction medium by extracting 3–15% hydrochloric acid, followed by precipitating the base of 2-methylamino-2-ethyldinanedione-1,3 with aqueous ammonia and turning it into a hydrochloride with a known method. The yield of the target product is 16%.
Предлагаемый способ позвол ет увеличить выход больше, чем в два раза, кроме того, он проще в исполнении, так как при его использовании не требуетс насыщени реакционной массы хлористым водородом дл выделени гидрохлорида или оксалата 2-метиламино-2-этилиндандиона-1 ,3.The proposed method makes it possible to increase the yield by more than two times; moreover, it is simpler to perform, since using it does not require saturation of the reaction mass with hydrogen chloride to isolate the hydrochloride or 2-methylamino-2-ethylandanedione-1, 3 oxalate.
Пример 1. Гидрохлорид-2-метиламино-2этилиндандион-1 ,3.Example 1. Hydrochloride-2-methylamino-2-ethylindic-1, 3.
К 600 мл бензольного раствора 2-бром- этилиндандиона-1,3, который получен из кпропилиденфталида (синтезированного, ис.ход из 148 г 1 .моль фталевого ангидрида), после отделени хлористого кальци добавл ютTo 600 ml of benzene solution of 2-bromoethylindandione-1,3, which is obtained from propylidenephthalide (synthesized, using 148 g of 1. Mole of phthalic anhydride), after separation of calcium chloride, add
140-200 мл диметилформамида или диметилсульфоксида и потом сразу же насыщают 31,8 г сухого мет1 ламина при температуре в массе около 10°С по приросту веса. Необходимое количество метиламина рассчитывают по расходу брома при бромировании, счита , что на 1 моль бромида (253 г) нужно ввести в реакцию 2 моль (62 г) метиламина. Колбу закрывают и оставл ют при ко.мнатной температуре (реакциопна масса имеет темнокрасный цвет), выпадает гидробромид метиламина и содержимое колбы незначительно разогреваетс . На следующий день обрабатывают но известному способу. Выход 36 г (15,0% от теоретического, счита на фталевый ангидрид) белого кристаллического вещсства с т. разл. 226-228°С (из абсолютного этанола с добавлением эфира или петролейного эфира).140-200 ml of dimethylformamide or dimethyl sulfoxide and then immediately saturated with 31.8 g of dry methane laminate at a mass temperature of about 10 ° C in terms of weight gain. The required amount of methylamine is calculated from the consumption of bromine during bromination, considering that per mole of bromide (253 g), 2 mol (62 g) of methylamine must be introduced into the reaction. The flask is closed and left at room temperature (the reaction mass is dark red), methylamine hydrobromide precipitates and the contents of the flask are slightly heated. The next day, but the process is known. Output 36 g (15.0% of theoretical, counted on phthalic anhydride) of a white crystalline substance with t. 226-228 ° C (from absolute ethanol with the addition of ether or petroleum ether).
Пример 2. Гидрохлорид-2-метиламиио-2этилиндандиои-1 ,3.Example 2. Hydrochloride-2-methylamio-2 ethylindandi-1, 3.
Реакцию 2-бром-2-этилиндандио 1а-1,3 с метиламином провод т так же, как в примере 1. На следующий день отдел ют гидробромид метиламина и фильтрат нромывают 2-3 раза по 350 мл воды. Органическую часть экстрагируют 2 раза разбавленной сол ной кислотой (1:4), иснользу всего 350 мл разбавленпой сол ной кислоты. Кислые выт жки соедин ют и медленно довод т до рН 8-9 прибавлением около 65 мл 25%-ного водного аммиака при охлаждении лед ной водой. Осадок отдел ют через 2-3 час, промывают водой. Выход основани после сушки от 38- 42 г (желтое вещество с т. пл. 102-104°С). Вещество раствор ют в 350 мл бензола и в раствор пропускают газообразный хлористый водород до окончани образовани осадка, после 1-2 час соль отдел ют, выход 37-41 г (15,4-17,1% от теоретического, счита на фталевый ангидрид); белое кристаллическое The reaction of 2-bromo-2-etilindandio 1a-1,3 with methylamine is carried out as in Example 1. The next day, methylamine hydrobromide is separated and the filtrate is washed with 2-3 ml of water 350 ml. The organic portion is extracted 2 times with diluted hydrochloric acid (1: 4), using only 350 ml of dilute hydrochloric acid. The acidic extracts are combined and slowly brought to pH 8-9 by adding about 65 ml of 25% aqueous ammonia while cooling with ice water. The precipitate is separated after 2-3 hours, washed with water. The yield of the base after drying is from 38 to 42 g (a yellow substance with a melting point of 102-104 ° C). The substance is dissolved in 350 ml of benzene and hydrogen chloride gas is passed into the solution until a precipitate forms, after 1-2 hours the salt is separated, yield 37-41 g (15.4-17.1% of theoretical, considering phthalic anhydride) ; white crystalline
вещество с т. разл. 226-228°С после кристаллизации из абсолютного этанола с добавлением эфира или петролейного эфира.substance with t. dec. 226-228 ° C after crystallization from absolute ethanol with the addition of ether or petroleum ether.
N 5,92; С1 N 5.92; C1
Найдено, %: С 60,21; Н 5,75; 14,90. N 5,84: С1Found,%: C 60.21; H 5.75; 14.90. N 5.84: C1
Вычислено, %: С 60,13; Н 5,88: 14,80.Calculated,%: C 60.13; H 5.88: 14.80.
Предмет изобретени Subject invention
Claims (2)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU1609913A SU369793A1 (en) | 1971-01-19 | 1971-01-19 | |
SE00543/72A SE367397B (en) | 1971-01-19 | 1972-01-18 | |
CA132,738A CA993890A (en) | 1971-01-19 | 1972-01-18 | Method of producing 2-methylamino-2-ethylindandi-1,3-one hydrochloride |
NL7200750A NL7200750A (en) | 1971-01-19 | 1972-01-19 | |
CH78772A CH560674A5 (en) | 1971-01-19 | 1972-01-19 | |
GB260571A GB1334322A (en) | 1971-01-19 | 1972-01-19 | Method of producing 2-methylamino-2-ethylindandi-1,3-one hydrochloride |
DE19722202456 DE2202456A1 (en) | 1971-01-19 | 1972-01-19 | Process for the preparation of 2-methylamino-2-ethylindane-1,3-dione hydrochloride |
FR7201693A FR2122956A5 (en) | 1971-01-19 | 1972-01-19 | |
BE778225A BE778225A (en) | 1971-01-19 | 1972-01-19 | METHOD FOR PREPARING 2 METHYLAMINO HYDROCHLORIDE 2-ETHYL INDANDIONE-1,3 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU1609913A SU369793A1 (en) | 1971-01-19 | 1971-01-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
SU369793A1 true SU369793A1 (en) | 1974-03-15 |
Family
ID=20463358
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SU1609913A SU369793A1 (en) | 1971-01-19 | 1971-01-19 |
Country Status (9)
Country | Link |
---|---|
BE (1) | BE778225A (en) |
CA (1) | CA993890A (en) |
CH (1) | CH560674A5 (en) |
DE (1) | DE2202456A1 (en) |
FR (1) | FR2122956A5 (en) |
GB (1) | GB1334322A (en) |
NL (1) | NL7200750A (en) |
SE (1) | SE367397B (en) |
SU (1) | SU369793A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS609742B2 (en) * | 1979-07-17 | 1985-03-12 | 昌明 伊藤 | 2-(N,N-dimethylamino)indan-1,3-dione and its production method |
-
1971
- 1971-01-19 SU SU1609913A patent/SU369793A1/ru active
-
1972
- 1972-01-18 CA CA132,738A patent/CA993890A/en not_active Expired
- 1972-01-18 SE SE00543/72A patent/SE367397B/xx unknown
- 1972-01-19 BE BE778225A patent/BE778225A/en unknown
- 1972-01-19 DE DE19722202456 patent/DE2202456A1/en active Pending
- 1972-01-19 FR FR7201693A patent/FR2122956A5/fr not_active Expired
- 1972-01-19 GB GB260571A patent/GB1334322A/en not_active Expired
- 1972-01-19 NL NL7200750A patent/NL7200750A/xx unknown
- 1972-01-19 CH CH78772A patent/CH560674A5/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FR2122956A5 (en) | 1972-09-01 |
NL7200750A (en) | 1972-07-21 |
DE2202456A1 (en) | 1972-10-26 |
SE367397B (en) | 1974-05-27 |
GB1334322A (en) | 1973-10-17 |
CH560674A5 (en) | 1975-04-15 |
CA993890A (en) | 1976-07-27 |
BE778225A (en) | 1972-07-19 |
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