JPS60252431A - Production of conjugated unsaturated compound - Google Patents
Production of conjugated unsaturated compoundInfo
- Publication number
- JPS60252431A JPS60252431A JP59110231A JP11023184A JPS60252431A JP S60252431 A JPS60252431 A JP S60252431A JP 59110231 A JP59110231 A JP 59110231A JP 11023184 A JP11023184 A JP 11023184A JP S60252431 A JPS60252431 A JP S60252431A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- tert
- formula
- conjugated unsaturated
- 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
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 150000003457 sulfones Chemical class 0.000 claims abstract description 8
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 125000006239 protecting group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000002411 adverse Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- -1 triene compound Chemical class 0.000 abstract description 3
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 abstract description 2
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 abstract description 2
- 230000006326 desulfonation Effects 0.000 abstract description 2
- 238000005869 desulfonation reaction Methods 0.000 abstract description 2
- 238000005906 dihydroxylation reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 235000019155 vitamin A Nutrition 0.000 abstract description 2
- 239000011719 vitamin A Substances 0.000 abstract description 2
- 229940045997 vitamin a Drugs 0.000 abstract description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007858 starting material Substances 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FVJPIFWJQUIPNO-UHFFFAOYSA-N 2-methylpropan-2-ol;oxolane Chemical compound CC(C)(C)O.C1CCOC1 FVJPIFWJQUIPNO-UHFFFAOYSA-N 0.000 description 1
- 101150030723 RIR2 gene Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の技術分野）
本発明は共役した炭素、炭素不飽和結合を有する化合物
の新規製法に関する。DETAILED DESCRIPTION OF THE INVENTION (Technical Field of the Invention) The present invention relates to a novel method for producing compounds having conjugated carbon-carbon unsaturated bonds.
（従来の技−術）
共役した炭素、炭素不飽和結合を有する化合物は有機半
導体への特性から興味ある物質であり、またイソプレノ
イド系の共役ポリエン化合物はビタミンＡの前駆物質或
いはその他の生理活性物質もしくはそれらの前駆体とし
て重要である。(Prior art) Compounds having conjugated carbon or carbon unsaturated bonds are interesting substances because of their properties as organic semiconductors, and isoprenoid-based conjugated polyene compounds are precursors of vitamin A or other physiologically active substances. Or they are important as their precursors.
従来このような共役不飽和化合物の製法としでは、段階
的な二重結合もしくは三重結合の生成或いは炭素−炭素
結合の形成による共役鎖の延長等合成的に不便な方法し
か知られていない。Conventionally, only synthetically inconvenient methods are known for producing such conjugated unsaturated compounds, such as stepwise formation of double or triple bonds or elongation of conjugated chains by formation of carbon-carbon bonds.
（発明の目的）
本発明は、スルホニル基に対してβ−位置に、保護され
たヒドロキシ基を有する化合物を用いで、脱スルホン化
と脱ヒドロキシ化を簡便で且つ穏和な条ｎ下で一挙に行
い、有用な共役不飽和化合物を容易に合成する方法を提
供するものである。(Objective of the Invention) The present invention facilitates desulfonation and dehydroxylation at once under mild conditions using a compound having a protected hydroxy group at the β-position relative to the sulfonyl group. The present invention provides a method for easily synthesizing useful conjugated unsaturated compounds.
（発明の構成）
本発明は、スルホニル基に対してβ位置に、保護された
ヒドロキシ基を有する下記一般式（Ｉ）で表わされるス
ルホン類を第三ブトキシカリウムで処理することを特徴
とする共役不飽和化合物の製法である。(Structure of the Invention) The present invention provides a conjugation method characterized in that a sulfone represented by the following general formula (I) having a protected hydroxy group at the β position with respect to a sulfonyl group is treated with potassium tert-butoxy. This is a method for producing unsaturated compounds.
Ｏ２Ｒ
ＯＲ５ＨＲ４
但し、上記（Ｉ＞式において、Ｙは−ＣＨ＝ＣＨ−又は
−ＣミＣ−１Ｒはアリール基、ＲＩＲ２は第三ブトキシ
カリウムによる処理に対しで不活性であって本反応に悪
影響を及ぼさない置換基を有していてもよい炭化水素基
、Ｒ３゜Ｒ４は水素又はＲ＋ 、Ｒ２と同様に定義され
る基で同一であってもよい。Ｒ５はヒドロキシ基の保護
基、πはＯ又は正整数である。O2R OR5HR4 However, in the above formula (I>, Y is -CH=CH- or -CmiC-1R is an aryl group, and RIR2 is inert to treatment with tert-butoxypotassium and does not have an adverse effect on this reaction. A hydrocarbon group that may have a substituent that does not have any effect, R3゜R4 is hydrogen or R+, and may be the same group as defined in R2. R5 is a protecting group for a hydroxy group, π is O or a positive integer.
本発明を反応式で示すと下記（Ｉｔ）式のように表わさ
れる。The present invention is represented by the following reaction formula (It).
上記（Ｉ［＞式のように、本発明は出発物質であるスル
ホン類の炭素骨格中の不飽和結合の共役鎖を２ケ延長す
る合成法といえる。例えば、１−〇の場合はジエン化合
物が生成し、１＝１の場合は、Ｙが二重結合のとぎは生
成物はトリエン化合物となり、Ｙが三重結合のときはエ
ン−イン−エン化合物が生成する。また本発明の犬、ぎ
な特徴として、生成する二重結合はトランス型異性体の
生成率が極めて高いことであり、化合物によっては実質
的に１００％のトランス型生成率を示すものがある。As shown in the above formula (I is produced, and when 1=1, when Y is a double bond, the product is a triene compound, and when Y is a triple bond, an en-yn-ene compound is produced. A characteristic feature is that the double bond produced has an extremely high production rate of the trans isomer, and some compounds show a substantially 100% production rate of the trans isomer.
本発明において、出発物質として用いられるβ−位置に
、保護されたヒドロキシ基を有するスルボン類は、例え
ば下記（Ｉ［［）式に示されるように適当なスルホニル
基を有する化合物とアルデヒドとの付加によって容易に
合成することができる。In the present invention, the sulfones having a protected hydroxyl group at the β-position used as starting materials can be prepared by, for example, adding a compound having a suitable sulfonyl group with an aldehyde as shown in the following formula (I[[)]. can be easily synthesized by
（Ｉ）式に従って説明すると、適当なスルホンを例えば
１−ブチル化リチウム（ｕ−ＢｕＬｉ）によってアニオ
ン化してアルデヒドと反応させ、得られたヒドロキシ化
合物を、例えば無水酢酸（ＡＣ２０）＋ピリジン（Ｐｙ
）を作用させる常法によってヒドロキシ基に保護基（ア
セチル基）を導入することができる。保護基としては、
有機合成反応で常用されるアセチル基、テトラヒドロピ
ラニル基等が任意に用いられる。According to formula (I), a suitable sulfone is anionized with, for example, 1-butylated lithium (u-BuLi) and reacted with an aldehyde, and the resulting hydroxy compound is converted into, for example, acetic anhydride (AC20) + pyridine (Py
) can be used to introduce a protective group (acetyl group) into the hydroxy group. As a protecting group,
Acetyl groups, tetrahydropyranyl groups, etc. commonly used in organic synthesis reactions can be optionally used.
ｙ
Ｏ２Ｒ
ＯＡｃ ＨＲ’
本発明のポリエン形成反応は、前記（Ｉ［）式に示した
ように、スルホニル基とβ−ヒドロキシ基の脱離反応に
よるものであり反応は極めて容易である。即ち、出発物
質であるスルホン類をテトラヒドロフランもしくはテト
ラヒドロ７ランー第三ブタノール混合物等を溶媒として
第三ブトキシカリウムを作用させることによって目的が
達成される。y O2R OAc HR' The polyene forming reaction of the present invention is based on the elimination reaction of a sulfonyl group and a β-hydroxy group, as shown in formula (I[) above, and the reaction is extremely easy. That is, the object is achieved by treating the starting material sulfone with potassium tert-butoxy using tetrahydrofuran or a mixture of tetrahydrofuran-tert-butanol as a solvent.
第三ブトキシカリウムは、スルホン１モルに対して当量
以上、通常２．５〜１５モル程度使用される。反応温度
は室温乃至還流温度で十分であり、反応時間は使用する
スルホン類によって異なり特に制限されない。Potassium tert-butoxy is used in an amount equivalent to or more, usually about 2.5 to 15 moles, per mole of sulfone. A reaction temperature of room temperature to reflux temperature is sufficient, and the reaction time varies depending on the sulfone used and is not particularly limited.
（実施例）
実施例１〜７
表１に示す出発物質を用いて対応する共役不飽和化合物
を製造した。(Example) Examples 1 to 7 Using the starting materials shown in Table 1, corresponding conjugated unsaturated compounds were produced.
表中、ｔ −ＢＵ ＯＫ （第三ブトキシカリウム）モ
ル比はｔ −Ｂｕ ＯＫ／出発物質で表わした。In the table, the t-BU OK (potassium tert-butoxy) molar ratio is expressed as t-Bu OK/starting material.
生成物の収率はカラムクロマトグラフィ精製による値で
ある。また、ＴＨＦはテトラヒドロフラン、ｔ−Ｂｌｏ
ｔ−Ｎｌ第三ブタノール、１− ＨＰはテトラヒドロフ
ラニル基、ｐｈはフェニル基、ＡＣはアセチル基、（ｙ
ｌｅはメチル基をそれぞれ表わす。Product yields are values obtained by column chromatography purification. In addition, THF is tetrahydrofuran, t-Blo
t-Nl tert-butanol, 1-HP is a tetrahydrofuranyl group, ph is a phenyl group, AC is an acetyl group, (y
le each represents a methyl group.
実施例１〜７の生成物の核磁気共鳴スペクトルは次のと
ありであった。The nuclear magnetic resonance spectra of the products of Examples 1-7 were as follows.
実施例１： ’ＨＮＭＲ（ＣＣＩ ４ ）δ０，７６−
１．１３ （ｍ 、３Ｈ，ＣＨ３） 。Example 1: 'HNMR (CCI4) δ0,76-
1.13 (m, 3H, CH3).
１．００ （（１、６Ｈ，Ｃ（ＣＨ３）２ 、 Ｊ＝
６．８Ｈ７）。1.00 ((1,6H,C(CH3)2, J=
6.8H7).
１．２７−１．７０ （ｎ＋ 、 ８Ｈ，ＣＨ２） 、
１．７６−２．６１ （ｎ＋ 、 ３Ｈ。1.27-1.70 (n+, 8H, CH2),
1.76-2.61 (n+, 3H.
４Ｈ２） 、１．００−１．５０ （ＩＩＩ 、 ＩＯ
Ｈ，ＣＨ２） 、１．５０−２．２０（ｍ 、 ２ｆ−
（、ＣＨ２Ｃ＝Ｃ） 、 ４．６０−６．４０ （ｍ
、 ５Ｈ，Ｃ＝ＣＨ２、Ｃ＝ＣＨ） 、 Ｉ３ＣＮＭＲ
（ＣＤＣＩ ｓ ）δ１１４．５゜１３０．９． １３
５．６．１３７．４ （ｏｌｅｆｉｎｉｃ ｃａｒｂｏ
ｎｓ ） 。4H2), 1.00-1.50 (III, IO
H, CH2), 1.50-2.20(m, 2f-
(, CH2C=C), 4.60-6.40 (m
, 5H, C=CH2, C=CH), I3CNMR
(CDCIs) δ114.5°130.9. 13
5.6.137.4 (olefinic carbo
ns).
実施例３： ’ＨＮＭＲ（ＣＣＩ ４）６１，００ （
ｄ 、６Ｈ，Ｃ（ＣＩ−１３）２ 。Example 3: 'HNMR (CCI 4) 61,00 (
d,6H,C(CI-13)2.
Ｊ＝ ６．８Ｈｚ ）、 １．３４ （ｓ 、 １．８
０ Ｈ，Ｃｌ−１３）、 １．４１（ｓ 、 １，２０
Ｈ，ＣＨ３＞、 ２．００−２．６０ （ｍ 、 Ｉ
Ｈ，ＣＨＣ＝Ｃ） 、 ３．８０ （ｓ 、 ４Ｈ，０
ＣＨ２ＣＨ２０） 、 ５．００−７．００（ｍ 、
４Ｈ，ＣＨ＝ＣＨ） 。J = 6.8Hz), 1.34 (s, 1.8
0 H, Cl-13), 1.41(s, 1,20
H, CH3>, 2.00-2.60 (m, I
H,CHC=C), 3.80 (s, 4H,0
CH2CH20), 5.00-7.00(m,
4H, CH=CH).
実施例４： ’ＨＮＭＲ（ＣＣＩ ４）δ０，７９ （
ｔ 、３Ｈ，ＣＨ３、Ｊ＝４１−（Ｚ ）、 ０．９５
−１．７０（ｍ 、 １４Ｈ，ＣＨ２）、 ｉ、８０
（ｓ 。Example 4: 'HNMR (CCI 4) δ0,79 (
t, 3H, CH3, J=41-(Z), 0.95
-1.70 (m, 14H, CH2), i, 80
(s.
６１−１． ＣＨ３）、 ２．４２ （ｔ、 ２Ｈ，Ｃ
Ｈ３ＣＯ，Ｊ＝７Ｈ２）。61-1. CH3), 2.42 (t, 2H,C
H3CO, J=7H2).
５．８０ （ｄ 、 １１−１． Ｃ＝ＣＨＣ＝ＣＣ０
，Ｊ＝１２Ｈｚ ）、 ５．９０（ｄ 、ＩＨ，Ｃ＝Ｃ
ＨＣ０，Ｊ＝１５Ｈｚ ）、７．２７ （ｄｄ、１１−
１゜Ｃｌ−１＝ｃｃｏ、 Ｊ＝１５．１２）−１２）
。5.80 (d, 11-1. C=CHC=CC0
, J=12Hz), 5.90(d, IH, C=C
HC0, J=15Hz), 7.27 (dd, 11-
1°Cl-1=cco, J=15.12)-12)
.
実施例５： ＩＨＮＭＲ（ＣＣＩ ａ ）６１，００
（ｄ 、６１→、Ｃ（ＣＨ３）２゜Ｊ＝ ６Ｈｚ ）
、 ０．７０−１．００ （ｍ 、 ３Ｈ，ＣＨ３）
、 １．１１−１．５９（ｍ 、 ４Ｈ，ＣＨ２） 、
１．８０−２．６０ （ｍ 、 ３１−１． ＣＨＣ
＝Ｃ。Example 5: IHNMR (CCI a) 61,00
(d, 61→, C(CH3)2゜J=6Hz)
, 0.70-1.00 (m, 3H, CH3)
, 1.11-1.59 (m, 4H, CH2),
1.80-2.60 (m, 31-1.CHC
=C.
ＣＨ２Ｃ＝Ｃ） 、 ５．００−６．４（１（ｍ 、
６Ｈ，Ｃｌ−１＝ＣＨ） 。CH2C=C), 5.00-6.4(1(m,
6H, Cl-1=CH).
実施例６： ’ＨＮＭＲ（ＣＣＩ ａ ）δ１．５０
（ｓ 、３Ｈ，ＣＨ３） 、１．５８（ｓ、３Ｈ，ＣＨ
ａ ＞、１．６８ （ｓ、６Ｈ，ＣＨ３）、１．７９（
ｓ 、３ｔ−１，Ｃｌ−１３＞、１．９０−２．２０
（ｍ 、４Ｈ，ＣＨ２Ｃ＝Ｃ） 。Example 6: 'HNMR (CCI a) δ1.50
(s, 3H, CH3), 1.58 (s, 3H, CH
a >, 1.68 (s, 6H, CH3), 1.79 (
s, 3t-1, Cl-13>, 1.90-2.20
(m, 4H, CH2C=C).
４．７０−５．１５ （ｍ 、ＩＨ，Ｃ＝Ｃ）−１）
、５．５８−６．６０ （ｍ 、７Ｈ。4.70-5.15 (m, IH, C=C)-1)
, 5.58-6.60 (m, 7H.
Ｃ＝ＣＨ）。C=CH).
実施例７： ’ＨＮＭＲ（ＣＣＩ ａ ）δ０，７０−
１．０５ （Ｉｌｌ 、３Ｈ，Ｃｌ−１３） 。Example 7: 'HNMR (CCI a) δ0,70-
1.05 (Ill, 3H, Cl-13).
０．９４ （ｄ 、６Ｈ，Ｃ（ＣＨ３）２ 、 Ｊ＝
６．８Ｈｚ ）。0.94 (d, 6H, C(CH3)2, J=
6.8Hz).
１．０７−ｔ６３ （ｍ 、８Ｈ，ＣＨ２） 、２．０
０−２．４５ （ｎ＋ 、３Ｈ。1.07-t63 (m, 8H, CH2), 2.0
0-2.45 (n+, 3H.
ＣＨＣ＝Ｃ，ＣＨ２Ｃ−Ｃ） 、５．１１−６．５７
（ｍ 、４Ｈ。CHC=C, CH2C-C), 5.11-6.57
(m, 4H.
ＣＨ＝ＣＩ−１）。CH=CI-1).
出願人 大阪曹達株式会社 代理人 弁理士 門多 透Applicant: Osaka Soda Co., Ltd. Agent: Patent Attorney Toru Kadota
Claims (1)
基を有する下記一般式（Ｉ）で表わされるスルホン類を
第三ブトキシカリウムで処理することを特徴とする共役
不飽和化合物の製法。 ０２ Ｒ ＯＲ５ＨＲ４ 但し、（Ｉ）式において、Ｙは一〇 Ｈ＝ ＣＩ−（−
又は−Ｃ＝Ｃ−１Ｒはアリール基、Ｒ１、Ｒ２は第三ブ
トキシカリウムによる処理に対して不活性であって本反
応に悪影響を及ぼさない置換基を有していてもよい炭化
水素基、Ｒ３、Ｒ４は水素又はＲ１、Ｒ２と同様に定義
される基で同一であってもよい。Ｒ５はヒドロキシ基の
保護基、ＴｈはＯ又は正整数である。[Claims] A conjugated unsaturated compound characterized in that a sulfone represented by the following general formula (I) having a protected hydroxy group at the β position relative to a sulfonyl group is treated with potassium tert-butoxy. manufacturing method. 02 R OR5HR4 However, in formula (I), Y is 10 H= CI-(-
or -C=C-1R is an aryl group, R1 and R2 are hydrocarbon groups which may have a substituent that is inert to the treatment with tert-butoxypotassium and does not adversely affect this reaction, R3 , R4 may be hydrogen or groups defined similarly to R1 and R2 and may be the same. R5 is a hydroxy protecting group, and Th is O or a positive integer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59110231A JPS60252431A (en) | 1984-05-29 | 1984-05-29 | Production of conjugated unsaturated compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59110231A JPS60252431A (en) | 1984-05-29 | 1984-05-29 | Production of conjugated unsaturated compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60252431A true JPS60252431A (en) | 1985-12-13 |
| JPH0355451B2 JPH0355451B2 (en) | 1991-08-23 |
Family
ID=14530417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59110231A Granted JPS60252431A (en) | 1984-05-29 | 1984-05-29 | Production of conjugated unsaturated compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60252431A (en) |
-
1984
- 1984-05-29 JP JP59110231A patent/JPS60252431A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0355451B2 (en) | 1991-08-23 |
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