SU506291A3 - The method of producing sulfones - Google Patents

The method of producing sulfones

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Publication number
SU506291A3
SU506291A3 SU1998403A SU1998403A SU506291A3 SU 506291 A3 SU506291 A3 SU 506291A3 SU 1998403 A SU1998403 A SU 1998403A SU 1998403 A SU1998403 A SU 1998403A SU 506291 A3 SU506291 A3 SU 506291A3
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SU
USSR - Soviet Union
Prior art keywords
general formula
compound
conjugated
equal
alkyl
Prior art date
Application number
SU1998403A
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Russian (ru)
Inventor
Шабардэс Пьер
Жюлиа Марк
Менэ Альбер
Original Assignee
Рон-Пуленк С.А. (Фирма)
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Publication of SU506291A3 publication Critical patent/SU506291A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/22—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

(54) СПОСОБ ПОЛУЧЕНИЯ СУЛЬФОНОВ(54) METHOD FOR OBTAINING SULFONS

1212

где R, Q имеют вышеуказанные значени , с последующим выделением целевого продукта известным способом.where R, Q are as defined above, followed by isolation of the target product in a known manner.

Сведени  о способе получени  соединений формулы I в литературе отсутствуют.Information about the method of obtaining compounds of the formula I is absent in the literature.

Предлагаемый способ получени  соединений формулы I заключаетс  в том, что соединение общей формулыThe proposed method for the preparation of compounds of formula I is that the compound of the general formula

Ш, SOjRW, SOjR

j 3 , j 3,

Л/L /

подвергают взаимодействию с interact with

соединением общей формулыcompound of general formula

СН  1 С СНСН 1 С СН

, ,

сы; снsy; sn

где R, RI и А имеют вышеуказалные значени , в присутствии щелочного агента с последующим выделением целевого продукта известным способом.where R, RI and A are as defined above, in the presence of an alkaline agent, followed by isolation of the target product in a known manner.

Реакци  протекает по следующей схеме:The reaction proceeds as follows:

S02RS02R

SOjK,SOjK,

JJJj

Эту реакцию конденсации диеновых соединений с сульфоном осуществл ют в присутствии щелочных минеральных или органических агентов, таких, как гидроокиси или алкогол ты щелочных металлов, амины, например диэтиламин, диизопропиламин, пиридин , триэтиламин, трибутиламин, гидроокиси четвертичного аммони . Реакци  ,может быть проведена в среде растворител  или без него , но предпочтительнее использовать такой растворитель, чтобы реакци  протекала в гомогенной фазе. Таким растворителем может быть спирт, налример метанол, этанол, третбутанол , или простой эфир, такой, как диэтиловый эфир, диоксан, тетрагидрофуран, или другой инертный растворитель, в частности бензол, толуол, диметилформа;мид, ацетонитрил .This condensation reaction of diene compounds with sulfone is carried out in the presence of alkaline mineral or organic agents, such as alkali metal hydroxides or alkoxides, amines, such as diethylamine, diisopropylamine, pyridine, triethylamine, tributylamine, and quaternary ammonium hydroxide. The reaction may be carried out with or without a solvent, but it is preferable to use such a solvent so that the reaction proceeds in a homogeneous phase. Such a solvent may be an alcohol, nanolimer methanol, ethanol, tert-butanol, or an ether such as diethyl ether, dioxane, tetrahydrofuran, or another inert solvent, in particular benzene, toluene, dimethyl form; mid, acetonitrile.

Реакцию целесообразно проводить при комнатной темлературе, а в случае, .когда продукты реакции не измен ютс  при -нагревании , лшжно и при более высокой температуре .The reaction is expediently carried out at room temperature, and in the case when the reaction products do not change upon heating, it is better at a higher temperature.

Пример 1. В трехгорлую колбу емкостью 50 мл, снабженную капельной воронкой , холодильником и трубкой дл  подвода азота, загружают раствор 4,31 г (трцметил2 ,6,6 - оксо-3 - циклогексен-1 - ил)-5 - метил-3фе1 илсульфонил-1-пентадиена-2 ,4 в 20мл ацетонитрила , а затем 0,2 г гидроокиси трилт-етилбензиламмони  в виде раствора в 3 мл ацетонитрила . Далее в .колбу вливают в течение 10 мин раствор 2,1 г фенилсульфонил-1-метил3-бутадиена в 10 жл ацетонитрила и выдерживают смесь при перемешивании в течение нескольких часов при комнатной температуре, после чего реакционную массу выливают в смесь 200мл воды со 100мл диэтилового эфира . Декантированный водный слой экстрагируют трижды по 100 мл эфира; объединенные эфирные слои промывают трижды по 100 мл воды, высушивают над сульфатом магни  иExample 1. In a three-neck flask with a capacity of 50 ml, equipped with an addition funnel, a condenser and a tube for supplying nitrogen, load a solution of 4.31 g (trcmethyl 2, 6.6 - oxo-3 - cyclohexen-1 - yl) -5 - methyl-3fe1 ylsulfonyl-1-pentadiene-2, 4 in 20 ml of acetonitrile, and then 0.2 g of triloethyl benzylammonium hydroxide as a solution in 3 ml of acetonitrile. Next, a solution of 2.1 g of phenylsulfonyl-1-methyl3-butadiene in 10 g of acetonitrile is poured into the flask for 10 minutes and kept the mixture under stirring for several hours at room temperature, after which the reaction mass is poured into a mixture of 200 ml of water with 100 ml of diethyl the ether. The decanted aqueous layer is extracted three times with 100 ml of ether; the combined ether layers are washed three times with 100 ml of water each, dried over magnesium sulphate and

, ,чЖхЛ WHL

концентрируют. Получают 6,1 г масла, в котором идентифицируют и определ ют методами ИК-спектроскопии,  дерного магнитного резонанса и тонкослойной хроматографии продукт , соответствующий формуле:concentrate. 6.1 g of oil are obtained in which the product corresponding to the formula is identified and determined by means of IR spectroscopy, nuclear magnetic resonance and thin layer chromatography.

SOaCgHjSOaCgHj

Степень превращени  61%; выход 54%.Conversion rate 61%; yield 54%.

(Триметил - 2,6,6 - оксо - 3 - циклогексен1-ил )-5-метил - З-фенилсульфонил-1-пентадиен-2 ,4 приготовл ют окислением (триметил2 ,6,6 - циклогексен - 1 - ил)-5 - метил - З-фенилсульфонил-1-пентадиена-2 ,4 с помощью метанерйодата натри .(Trimethyl - 2,6,6 - oxo - 3 - cyclohexen1-yl) -5-methyl - 3-phenylsulfonyl-1-pentadiene-2, 4 is prepared by oxidation (trimethyl 2, 6,6 - cyclohexene - 1 - yl) - 5 - methyl - 3-phenylsulfonyl-1-pentadiene-2, 4 with sodium methane iodate.

Фенилсульфонил-1 -метил-3-бутадиен получают взаимодействием фенилхлор-4-метил-Збутен-2-илсульфона с триэтиламином в бензоле . Указанный хлорсульфон, используемый в реакции, получают в результате взаимодействи  фенилсульфината натри  с дихлор-1,4-метил-2-бутеном-2 в эквимолекул рных количествах в безводном этаноле.Phenylsulfonyl-1-methyl-3-butadiene is obtained by reacting phenyl chloro-4-methyl-Z-butene-2-ylsulfone with triethylamine in benzene. Said chlorosulfone used in the reaction is obtained by reacting sodium phenylsulfinate with dichloro-1,4-methyl-2-butene-2 in equimolar amounts in anhydrous ethanol.

Claims (1)

Формула изобретени Invention Formula Способ получени  сульфонов общей формулыThe method of producing sulfones of the general formula сн, SOjB «и,Sn, SOjB “and, сн с .г sn with .g -ч.-h mj ш sojR,mj w sojR, где R и RI - одинаковые или различные и представл ют собой замещенные или незамещенные алкил, арилалкил или арил; А - углеводородный радикал, содержащий 5 +1 атомов углерода, где п равно О-5, который может быть насыщенным или ненасыщенным , полиеновым сопр женным и/или несопр женны;м , при п, равном 1-5, А может содержать функциональные или алкильные группы, при п, равном или выще 2, А может включать цикл, содержащий или несодержащий алкильные и/или функциональные группы , такие, как О или , которые могут быть свободными или защищенными, отличающийс  тем, что соединение общей формулы I с /-ч / А СН подвергают взаимодействию с соединением общей формулы снГ crf где R, Ri и А имеют вышеуказанные значени , в присутствии щелочного агента с последующим выделением целевого продукта известным способом.where R and RI are the same or different and are substituted or unsubstituted alkyl, arylalkyl or aryl; A is a hydrocarbon radical containing 5 +1 carbon atoms, where n is O-5, which can be saturated or unsaturated, polyene conjugated and / or non-conjugated; m, with n equal to 1-5, A can contain functional or alkyl groups with n equal to or even higher than 2, A may include a cycle containing or not containing alkyl and / or functional groups, such as O or, which may be free or protected, characterized in that the compound of general formula I with / - h / a CH is subjected to interaction with the compound of the general formula CH g crf where R , Ri and A are as defined above, in the presence of an alkaline agent, followed by isolation of the target product in a known manner.
SU1998403A 1972-04-10 1974-02-19 The method of producing sulfones SU506291A3 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7212477A FR2180152A6 (en) 1972-04-10 1972-04-10 1,5-dimethyl-1,5-hexadienylidene sulphone derivs - - intermediates for terpenes

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SU506291A3 true SU506291A3 (en) 1976-03-05

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CH (1) CH570977A5 (en)
DD (1) DD112991A5 (en)
FR (1) FR2180152A6 (en)
SU (1) SU506291A3 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2573074B1 (en) * 1984-11-13 1987-01-30 Rhone Poulenc Sante PROCESS FOR PREPARING RETINONITRILE

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FR2180152A6 (en) 1973-11-23
DD112991A5 (en) 1975-05-12
CH570977A5 (en) 1975-12-31

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