JPS60255740A - 1-ethyl-3-halogeno-tricyclo(2.2.1.02,6)heptane and its preparation - Google Patents
1-ethyl-3-halogeno-tricyclo(2.2.1.02,6)heptane and its preparationInfo
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- JPS60255740A JPS60255740A JP11156184A JP11156184A JPS60255740A JP S60255740 A JPS60255740 A JP S60255740A JP 11156184 A JP11156184 A JP 11156184A JP 11156184 A JP11156184 A JP 11156184A JP S60255740 A JPS60255740 A JP S60255740A
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Abstract
Description
【発明の詳細な説明】
本発明は新規なハロゲン化炭化水素、更に詳しくは次式
(D
(式中、又はCI又け13rを示し、波線〜〜は置換位
置がエキソ又はエンドでおることを示す)
で表わされる1−エチル−3−ハロゲノ−トリシクロ(
2,2,1,0”)ヘゾタン及びその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel halogenated hydrocarbon, more specifically, a compound of the following formula (D (in the formula, or CI straddle 13r, and the wavy line ~~ indicates that the substitution position is exo or endo). 1-ethyl-3-halogeno-tricyclo(
2,2,1,0'') Hezotan and its manufacturing method.
従来、次式([1)
で衣わされるエチリデンピシクロヘデテン(以下、r[
cBHJと略記する)は強酸の存在下、種々の付加反応
を生起すること、例えばカルメン酸〔特公昭49−30
105号、乃、Org 。Conventionally, ethylidene picyclohedetene (hereinafter r[
(abbreviated as cBHJ) undergoes various addition reactions in the presence of strong acids, such as carmenic acid [Japanese Patent Publication No. 49-30
No. 105, No. Org.
Kbim、、 13.2085(1977))、アルコ
ール(米国特許第4,308,159号)ろるいはイソ
シアン酸(特開昭49−11,222号)と反応させる
と、次の反応式に従って構造の異なる281の化合物(
1)及び(■)の混合物を生ずることが知られている。Kbim,, 13.2085 (1977)), alcohol (U.S. Pat. No. 4,308,159), or isocyanic acid (Japanese Patent Publication No. 11,222/1989), a structure is formed according to the following reaction formula. 281 compounds with different
It is known that a mixture of 1) and (■) is produced.
(II) (1) (IV)
(式中、Nu−は核基を示し、波線M)の意味は前記と
同じ)
斯かる実状において、本発明者はII!8Hへのハロダ
ン化水素の付加反応につ−て検討を行い、ガス状のハロ
ゲン化水素を反応せしめたか、(IV)の構造の化合物
と従来知られていない異性体との混合物が得られ、その
選択性には特に改善Fi、みられなかった。ところが、
IIBHKハロゲン化水素*t−反応せしめたところ、
意外にも(1)式の新規化合物のみが極めて選択的に、
しかも高収率で得られることを見出し、本発明を完成し
た。(II) (1) (IV) (In the formula, Nu- represents a nuclear group, and the meaning of the wavy line M is the same as above) In this actual situation, the present inventors have realized II! We investigated the addition reaction of hydrogen halide to 8H, and either reacted gaseous hydrogen halide or obtained a mixture of a compound with structure (IV) and a previously unknown isomer. No particular improvement in selectivity was observed. However,
IIBHK hydrogen halide*t-reacted,
Surprisingly, only the new compound of formula (1) very selectively
Moreover, they found that it can be obtained in high yield, and completed the present invention.
すなわち、本発明は中成で貴わされる1−エチル−3−
ハロゲノ−トリシクロ(2,2゜1.0!・6〕へブタ
ン、並びにその製造法を提供するものでるる。That is, the present invention deals with 1-ethyl-3-
The present invention provides halogeno-tricyclo(2,2°1.0!.6)hebutane and a method for producing the same.
本発明化合物(1)は、l1iBH1溶媒中又は無溶媒
で次式
(式中、Xは前記と同じ)
で表わされるハロゲン化水索酸と反応させること罠よっ
て製造される。The compound (1) of the present invention is produced by reacting with a halogenated hydrochloric acid represented by the following formula (wherein X is the same as above) in a l1iBH1 solvent or without a solvent.
本発明を実施するには、[CBHと塩酸又は臭化水素l
!を攪拌混合すればよい。塩酸のHOJ濃度は5〜36
%が、また臭化水Xw1のHBr濃度は5〜47%が好
まし埴。To carry out the present invention, [CBH and hydrochloric acid or hydrogen bromide]
! Just stir and mix. The HOJ concentration of hydrochloric acid is 5-36
%, and the HBr concentration of the bromide water Xw1 is preferably 5 to 47%.
ハロゲン化水素の量は、1nB11に対し当量以上めれ
ば良−が経済性、後処理の点から考えて当量ないし10
倍当iが好まし一〇反応温度は0℃〜100℃好ましく
は10℃〜50℃の範囲でbる。反応は無溶媒でも良い
か、反応終了後の分層の容易さを考えて溶媒を用−るの
が好ましい。溶媒として灯、例え#iD−へキサン、エ
ーテル、ベンゼン、トルエン、クロロホルム等が挙げら
れる。溶媒量Fi特に限定されないか、単離の際の容易
さを考慮して18Hに対し同容量から2倍容JIiか好
まし一〇叙上の如くして得られる反応生成物が(1)式
で示す構造でるること社次の事実により立征される、す
なわち、反応生成物はキャピラリーカラム(メチルシリ
コン、50m)を用いたガスクロマトグラフィー(Go
)に付すと2本のビークに分かれるCG)式中X=Br
:ac比、34/66、X=C1:G(3比、23/7
7)。The amount of hydrogen halide should be at least equivalent to 1nB11, but from the viewpoint of economy and post-processing, the amount should be between equivalent and 10%.
The reaction temperature is preferably 0°C to 100°C, preferably 10°C to 50°C. The reaction may be carried out without a solvent, or it is preferable to use a solvent in view of ease of layer separation after the reaction is completed. Examples of the solvent include lamps such as #iD-hexane, ether, benzene, toluene, chloroform, and the like. The amount of solvent Fi is not particularly limited, or in consideration of ease of isolation, it is preferably from the same volume to 2 times the volume of 18H JIi. It is established by the following fact that the structure shown by
), it is divided into two beaks (CG) where X=Br
:ac ratio, 34/66, X=C1:G (3 ratio, 23/7
7).
そして反応生成物のガスマス分析の結果よシ、この2本
のビークは−ずれもハロゲン原子を1個有する組成式〇
参H1,Xに対応し、か′:)2つのビークのiススベ
クトルが極めて類似してiることから、2種の異性体に
対応することが予想される。そこで反応生成物をリチウ
ム及びt−シタノールと反応させて脱/10グンするこ
とによシ炭化水素に導くと単一の化合物が得られた。更
にそのIIC−NMRスペクト〃は文献記載の次式(至
)
で表わされる化合物のl”c−NMRスペクトルと一致
した[ Zb、Org、Kbi!o、、 13.208
5(1977)]。従って、当該反応生成物線式(υで
示される構造の化合物でハロゲン原子の立体配置が異な
る2稽の化合物(エキン体及びエンド体)の混合物でろ
ると結論される。According to the results of gas mass analysis of the reaction products, these two beaks correspond to the compositional formula H1, Since they are very similar, it is expected that they correspond to two types of isomers. Therefore, a single compound was obtained by reacting the reaction product with lithium and t-sitanol and decomposing it to a hydrocarbon. Furthermore, its IIC-NMR spectrum matched the l''c-NMR spectrum of the compound represented by the following formula (to) described in the literature [Zb, Org, Kbi!o,, 13.208
5 (1977)]. Therefore, it is concluded that the reaction product has a structure represented by the linear formula (υ) and is a mixture of two compounds (Ekyne and Endo isomers) in which the steric configuration of the halogen atom is different.
本発明化合物(1)は反応性に富むハライドでろるのて
、例えば医薬、農薬、香料等の炭素母核又は修飾基とし
て使用しうる重要な中間体でるる。The compound (1) of the present invention is a highly reactive halide and is an important intermediate that can be used as a carbon core or a modifying group in, for example, pharmaceuticals, agricultural chemicals, fragrances, etc.
例えば次式(X)
0口
(式中、R1、R,け、例えば同−若しくは異なってメ
チル基又はエチル基を示す)
で表わされる化合物は、香料として重要でめることが知
られて−る(特開昭59−10536号)。そシテ、化
合物(X) tj4B13s9−tosa6号公報及び
特開昭59−10542号公報の記載によれば、次の反
応式に従って合成される。For example, a compound represented by the following formula (X) (wherein R1, R, and , for example, the same or different represent a methyl group or an ethyl group) is known to be important as a fragrance. (Japanese Patent Application Laid-Open No. 59-10536). According to the descriptions in tj4B13s9-tosa6 and JP-A-59-10542, compound (X) is synthesized according to the following reaction formula.
(Vl) (Vil)
1AjH4
一一一−→ (X)
(式中、XIは例えばクロル基、R#′i例えdエチル
基を示し、R,及びR21d、前記と同じ)更に化合物
(vl)の合成法にクーては、上記公開公報には記載さ
nていなりが、文献記載の方法によれば化合物(Vl)
は次式に従って合成される( Zb 、 Or g、
Khi m、 、見、 2085 (1977))。(Vl) (Vil) 1AjH4 -→ (X) (wherein, XI is, for example, a chloro group, R#'i, for example, d-ethyl group, R, and R21d are the same as above), and further compound (vl) The synthesis method for the compound (Vl) is not described in the above-mentioned publication, but according to the method described in the literature, the compound (Vl)
is synthesized according to the following formula (Zb, Or g,
Khim, , 2085 (1977)).
すなわち、KBHにカルメン酸全強酸の存在下付加させ
て得られる(XI)と(X[l)の混合物を蒸留等で分
別しπ後化合物(■)1:加水分解してアルコール(X
I)となし、更にこれt−酸化して得られる。That is, a mixture of (XI) and (X[l) obtained by adding carmenic acid to KBH in the presence of a strong acid is separated by distillation or the like, and after π, compound (■) 1 is hydrolyzed to form alcohol (X
I) and further t-oxidation thereof.
このように1従来、化合物(X) 1i−得るためには
、[CBHから7ステツデ金要し、しかも中間体(XI
)と011)’を分別しなければならないという煩雑な
操作を必要とした。In this way, conventionally, in order to obtain compound (X) 1i-, 7 steps were required from [CBH, and intermediate (XI
) and 011)', which required a complicated operation.
これに対し、本発明化合物(1)tj、 Bauvea
uli反応に何丁と(■)式の化合物が得られるので、
本発明によれば下式に従って[CBHから2ステツプで
化合物(■)t−1従ってE8Hから4ステツプで化合
物(X)を得ることができる。また本発明によれはノル
トリシクロ[12,1゜03・6〕ヘプタン骨格を有す
る化合物のみを選択的に合成できるため、実質的に収率
を高めることができ、更に途中で異性体を分別する必要
がなく有利に合成できる。On the other hand, the compound of the present invention (1) tj, Bauvea
Since a compound of the formula (■) is obtained in the uli reaction,
According to the present invention, according to the following formula, compound (■) t-1 can be obtained in two steps from CBH, and therefore compound (X) can be obtained in four steps from E8H. Furthermore, according to the present invention, only compounds having a nortricyclo[12,1゜03.6]heptane skeleton can be selectively synthesized, so the yield can be substantially increased, and there is no need to separate isomers during the process. can be synthesized advantageously.
HX I7DMF
(It)−→(D−刊(■)−→(■)−一→(X)(
式中、Xは前記と同じ。DMFij:ジメチルホルムア
ルデヒドを示す)
次に実施例及び参考例を挙げて本発明を説明する。HX I7DMF (It)-→(D-published (■)-→(■)-1→(X)(
In the formula, X is the same as above. DMFij: Dimethyl formaldehyde) Next, the present invention will be explained with reference to Examples and Reference Examples.
実施例1
1−エチル−3−ブロモ−トリシクロ〔2゜2、1 、
0”l’〕ヘゾタン:
zsa(120f、1モル)のエーテル(200d)溶
液に47%臭化水素酸(344t、HBr2モA/)を
激しく攪拌しつつ、呈温で2時間かけて加える。更に4
時間攪拌し九後、静置して有機層を水層から分離し、水
層からエーテル(100d)で3回抽出したものと一緒
にする。有機層は飽和食塩水(50tIlt)で2回、
飽和重曹水(50m/)で−回洗い、更に飽和食塩水(
50m)で2回洗った後、硫醗ナトリウムで乾燥する。Example 1 1-ethyl-3-bromo-tricyclo[2°2,1,
0"l']Hezotane: To a solution of zsa (120f, 1 mol) in ether (200d), 47% hydrobromic acid (344 t, HBr2 moA/) is added with vigorous stirring at room temperature over 2 hours. 4 more
After stirring for 9 hours, the organic layer was allowed to stand, separated from the aqueous layer, and combined with the aqueous layer extracted three times with ether (100 d). The organic layer was treated with saturated saline (50 tIlt) twice.
Wash twice with saturated sodium bicarbonate solution (50 m/), and then wash with saturated saline solution (
After washing twice with 50 m), dry with sodium sulfate.
次いで有機層カラエーテル全ロータリーエバ?レータ−
で除き、減圧蒸留により目的物169 F(仕込みlB
Hに対して収率84.0%)を得る。Next is the organic layer color ether all rotary eva? rater
and distilled under reduced pressure to obtain the target product 169F (preparation 1B
A yield of 84.0% based on H is obtained.
沸点: 88.0〜90.0℃/15mmHg元素分析
:
分析値:0.53.9%、H,6,7%計算値:C,5
4,(1、H,6,5%工R(液膜、 tym−’ )
: 3060(シC−E)”H−NMR(ODO7g
溶媒、TMB階I準、δ)〜0.93 ((H,、3重
IR)、1.1〜2.3(複雑な多重線)、4.0 (
OH−Br )
Go −Mass (相対強度):
GO分析では、キャピラリーカラム(メチルシリコン、
50m)t−用いる事によシ、2本のピークに分かれる
。それぞれのマス/9ターンは非常に類似しており、ブ
ロムのエンド。Boiling point: 88.0-90.0℃/15mmHg Elemental analysis: Analysis value: 0.53.9%, H, 6.7% Calculated value: C, 5
4, (1, H, 6,5% engineering R (liquid film, tym-')
: 3060 (C-E)”H-NMR (ODO7g
Solvent, TMB order I standard, δ) ~ 0.93 ((H,, triple IR), 1.1 ~ 2.3 (complex multiplet), 4.0 (
OH-Br) Go-Mass (relative intensity): For GO analysis, a capillary column (methyl silicon,
50m) By using t-, it is divided into two peaks. Each square/9 turn is very similar, Brom's end.
エキソの異性体のものでらる。It is an exo isomer.
ピーク1(oc比、31) 202(M++2.2)、200(M+、2)。Peak 1 (OC ratio, 31) 202 (M++2.2), 200 (M+, 2).
121(82)、105(58)、93(62)。121 (82), 105 (58), 93 (62).
91(91)、79(84)、66(100)。91 (91), 79 (84), 66 (100).
55(50)、43(43)
ピーク2(Go比、66%)
202(M++2.1)、200(M+、1)121(
80)、105(54)、93(62)。55 (50), 43 (43) Peak 2 (Go ratio, 66%) 202 (M++ 2.1), 200 (M+, 1) 121 (
80), 105(54), 93(62).
91(84)、79(80)、66(100)。91 (84), 79 (80), 66 (100).
55(52)、43(38)
11c −N MR(cDcls fil媒、TMS内
部標準、δC。55(52), 43(38) 11c-N MR (cDcls filtration medium, TMS internal standard, δC.
多重度): aCピーク2に相当する異性体のもの。Multiplicity): The isomer corresponding to aC peak 2.
11.8(q)、17.7(1,2L6(t)。11.8(q), 17.7(1,2L6(t).
24.0(d)、28.7(s)、32.0(t)。24.0(d), 28.7(s), 32.0(t).
34.7(t)、39.5(d)、57.6(d)実施
例2
1−エチ#−3−クロロ−トリシクロ
(2,2,1,0”+@)へゾクン:
1cBH(12of、 1モル)のエーテル(20〇−
)溶液に36%塩酸(2039、HCl2 モル)を激
しく攪拌しつつ、反応温度が著しく上昇しないように(
20〜30℃)適度に水で冷しながら1時間かけて加え
る。更に12時間攪拌した後、静置して有機層を水層か
ら分け、水層からエーテル(150−)で3回抽出した
ものと一緒にする。次−で有機層′に実施例1と同様に
洗浄、乾燥を行なった後、減圧蒸留によシ目的物141
f(仕込みICBHに対して収率90.1−)を得る。34.7(t), 39.5(d), 57.6(d) Example 2 1-Ethy#-3-chloro-tricyclo(2,2,1,0''+@)hezokun: 1cBH( 12of, 1 mol) of ether (200-
) Add 36% hydrochloric acid (2039, HCl2 mol) to the solution while stirring vigorously, making sure that the reaction temperature does not rise significantly (
(20-30℃) Add over 1 hour while cooling with water. After stirring for an additional 12 hours, the organic layer was separated from the aqueous layer by standing and combined with the aqueous layer extracted three times with ether (150-). Next, the organic layer' was washed and dried in the same manner as in Example 1, and the desired product 141 was removed by vacuum distillation.
f (yield 90.1- based on ICBH charged) is obtained.
沸点: s 9.0〜90.5℃/26mmHg元素分
析:
分析値:0,6L8%、H,8,6%
計算値;c、69.0%、H,8,4%工R(液膜、
clR−”) : 3070(シO−H)lH−NMR
(CD0h浴媒、TMS内部標準、δ)0.9 ((H
8,3重線)、l、2〜2.1(複雑な多重#)。Boiling point: s 9.0-90.5℃/26mmHg Elemental analysis: Analysis value: 0.6L8%, H, 8.6% Calculated value: c, 69.0%, H, 8.4% film,
clR-”): 3070 (SiO-H)lH-NMR
(CD0h bath medium, TMS internal standard, δ)0.9 ((H
8, triplet), l, 2-2.1 (complex multiplet #).
3.9(OH−Br)
Go−Mas日(相対強度)
キャピラリーカラム(メチルシリコンr som;を用
−7’jGO分析では、21!Iiの化合物の混合物で
めり、2つのマス/9ターンが非常に類似している事か
らクロルのエンド、エキソの異性体でおる事が判る。3.9 (OH-Br) Go-Mas Day (Relative Intensity) In the -7'j GO analysis using a capillary column (methyl silicon r som;, a mixture of compounds of 21! Since they are very similar, it is clear that they are endo and exo isomers of chlor.
ピークl (Go比、23%):
158(M”+2.5)、156(M+、16)#12
0(37)、105(61)、93(34)。Peak l (Go ratio, 23%): 158 (M”+2.5), 156 (M+, 16) #12
0 (37), 105 (61), 93 (34).
91(87)、79(67)、77(31)。91(87), 79(67), 77(31).
66(100)、65(31) ピーク2(Go比、77%): 158(M++2.5)、156(M”、16)。66 (100), 65 (31) Peak 2 (Go ratio, 77%): 158 (M++2.5), 156 (M'', 16).
120(38)、105(59)、93(34)。120 (38), 105 (59), 93 (34).
91(95)、79(62)、77(36)。91 (95), 79 (62), 77 (36).
66(100)、65(32)
t3c −N MR(cpcz、 @媒、TM8内部標
準、δC1多重度)
GCピーク2に相当する異性体のもの。66(100), 65(32) t3c-N MR (cpcz, @ medium, TM8 internal standard, δC1 multiplicity) Isomer corresponding to GC peak 2.
11.8(q)、17.3(a)、22.8(t)。11.8(q), 17.3(a), 22.8(t).
23.7(d)、28.4(s)、31.2(t)。23.7(d), 28.4(s), 31.2(t).
34.7(t)、39.4(d)、65.3(d)参考
例1
実施例1で得た1−エチル−3−ブロモ−トリシクロ[
2,2,1,glJヘプタン(10,0fs 49.8
mmol )”iびt@ rt−ブタノール(11,
Of、 148mmol)のTHF (20m)溶液に
Li片(L46 f、0.498グラム当量)を室温で
加えよく攪拌する。8時間攪拌した後、温度をTHFが
還流するまで上げ、30分間この温度で攪拌を続は氷冷
する。次に、氷冷下、注意深くメタノール(10d)全
滴下して過剰L1と反応させる。金i@Liが消失した
事を確認した抜水(ioolRt)をさらに滴下し、次
に、水層からD−ヘキサン(10011it)で生成物
を抽出する。抽出した有機層は、飽和食塩水で洗浄、硫
酸マグネシウムで乾燥処理して、常圧蒸留すると、13
8〜140℃の留分でエチルトリシクロ(2,2,。34.7(t), 39.4(d), 65.3(d) Reference Example 1 1-ethyl-3-bromo-tricyclo[
2,2,1,glJ heptane (10,0 fs 49.8
mmol)”ibit@rt-butanol (11,
Li pieces (L46 f, 0.498 gram equivalent) were added to a THF (20 m) solution of L46 f, 148 mmol) at room temperature and stirred well. After stirring for 8 hours, the temperature is increased until the THF refluxes, and the mixture is stirred at this temperature for 30 minutes, followed by ice cooling. Next, under ice-cooling, methanol (10d) was carefully added dropwise to react with excess L1. After confirming that gold i@Li has disappeared, extracted water (ioolRt) is further added dropwise, and then the product is extracted from the aqueous layer with D-hexane (10011it). The extracted organic layer was washed with saturated saline, dried over magnesium sulfate, and distilled under normal pressure.
Ethyltricyclo(2,2,.
1、QL・〕ヘゾタy3.49F(収$57.411)
が得られる。1.QL・] Hezota y3.49F (Sales $57.411)
is obtained.
このものC)”O−NMR分析を行えば、標品のエチル
トリシクロ[2,2,1,0”I4)へブタy [zb
、 Org、 Kbim、 、 15 (2)、 32
0 (1979) )のそれと全く一致し、構造が確認
された。If you perform O-NMR analysis on this product, you will find that the standard ethyltricyclo[2,2,1,0''I4)buty [zb
, Org, Kbim, , 15 (2), 32
(1979)), and the structure was confirmed.
1” O−N MR(CDCl、溶1.7M8内部標準
、δC1多重度):
12.4(ct)、16.1(d)、23.1(t)。1" O-N MR (CDCl, 1.7M8 internal standard, δC1 multiplicity): 12.4 (ct), 16.1 (d), 23.1 (t).
24.4(s)、31.8(11)、34.2(t)。24.4(s), 31.8(11), 34.2(t).
aS、4(t)
参考例2
1−エチルトリシクロ[2,2,1,0”°“〕へ〕ブ
タンー3−カル〆キシアルデヒド実施例1に従い合成旦
たl−エチに−3−プロモートリシフo (2,2−1
−0”’]ヘプタン(20,1?、100ミリモル)、
乾燥ジメチルホルムアミド(7,31f、100ミリモ
ル)及びリチウムサンド(5,10f17.3当量)全
乾燥Tay(40m)に加え超音波洗浄器(200!、
45KHz)t−使用して反応させる。反応開始時は激
しく発熱するので氷冷し、反応温度は40℃を超えない
より注意する。aS, 4(t) Reference Example 2 1-Ethyltricyclo[2,2,1,0"°"] to butane-3-cartoxyaldehyde Synthesized according to Example 1, 1-ethyl to -3-promote Rishif o (2,2-1
-0”']heptane (20,1?, 100 mmol),
Dry dimethylformamide (7,31f, 100 mmol) and lithium sand (5,10f, 17.3 eq.) in a completely dry Tay (40 m) plus an ultrasonic cleaner (200 m,
45KHz) t- to react. At the beginning of the reaction, heat is generated violently, so cool with ice and be careful not to let the reaction temperature exceed 40°C.
反応時間は15分程度である。The reaction time is about 15 minutes.
次に反応だ液に水冷下で5%塩Mに滴下し、未反応リチ
ウムを分解させた後、エーテル(300m)’i加えて
分層させ、エーテル層を飽和食塩水(50m)で3回洗
浄する。硫1j[−rグネシクムで乾燥したエーテル層
は減圧エバーレータ−で濃縮し、さらに減圧蒸留すると
、1−エチルトリシクロ〔2・2・1・gL“〕へ〕ブ
タンー3−カル〆キシアルデヒド6541(収率43.
6%)t−得る。Next, 5% salt M was added dropwise to the reaction solution under water cooling to decompose unreacted lithium, then ether (300 m) was added to separate the layers, and the ether layer was diluted with saturated brine (50 m) three times. Wash. The ether layer dried with sulfur 1j[-rgnesicum was concentrated in a vacuum evaporator and further distilled under reduced pressure to yield 1-ethyltricyclo[2.2.1.gL"]butane-3-cartoxyaldehyde 6541 ( Yield: 43.
6%) t-obtain.
沸点: 58.0〜60.0℃/lmmHg元素分析:
分析値: 0.80.0%、H,9,5%計算値:0,
80.0%、H,9,1
工R(f[膜+ 611− ’ ) :3o60(シc
−n)、1720(νc=o)”H−NMR(cvcl
z溶媒、TMB内部標準、δ)0.93 (OHs 、
3重量)、1.2〜1.7(複雑な多重III ) 、
2.3(−an−cHo )、 9.7(−+:ap
)Go−Mass (相対強度)
aC分析では、キャピラリーカラム(メチルシリコy、
50111)を用いる事にょシ2本のピークに分かれ、
それぞれのマス、(lターンが非常に類似している事が
ら、ホλミルのエンド、エキソの異性体でるる事が判る
。Boiling point: 58.0-60.0°C/lmmHg Elemental analysis: Analysis value: 0.80.0%, H, 9.5% Calculated value: 0,
80.0%, H, 9,1 Engineering R (f [membrane + 611-'): 3o60 (Si c
-n), 1720 (νc=o)”H-NMR (cvcl
z solvent, TMB internal standard, δ) 0.93 (OHs,
3 weight), 1.2-1.7 (complex multiplex III),
2.3(-an-cHo), 9.7(-+:ap
) Go-Mass (relative intensity) For aC analysis, a capillary column (methyl silico y,
50111), it is divided into two peaks,
Since the (l-turns) of each mass are very similar, it can be seen that there are endo and exo isomers of the homil.
ピーク1(ac比、58チ):
150(M 、5)、121(100)、103(27
)。Peak 1 (ac ratio, 58ch): 150 (M, 5), 121 (100), 103 (27
).
93(26)、91(42)、79(49)、77(2
6)。93 (26), 91 (42), 79 (49), 77 (2
6).
55(36)、43(24)、41(30)ピーク2(
Go比、42%):
150(M 、4)、121(100)、103(25
)。55 (36), 43 (24), 41 (30) peak 2 (
Go ratio, 42%): 150 (M, 4), 121 (100), 103 (25
).
93(31)、91(3g)、79(49)、77(2
6)。93(31), 91(3g), 79(49), 77(2
6).
55(36)、43(24)、41(29)参考例3
1!!8H(10(1,0,833モル)K塩化水素ガ
スを水冷下吹き込む。発熱によシ反応温度は上昇し、1
5℃になる。この温度を保つようガスの吹き込み速度全
調節する。Go分析で反応全追跡すると、3時間程度で
已BHのピークは完全に消失し、反応が完結したことが
判る。55 (36), 43 (24), 41 (29) Reference example 3 1! ! 8H (10 (1,0,833 mol) K hydrogen chloride gas is blown in under water cooling. Due to heat generation, the reaction temperature rises and 1
The temperature will be 5℃. Adjust the gas blowing speed to maintain this temperature. When the entire reaction was followed by Go analysis, the BH peak completely disappeared in about 3 hours, indicating that the reaction was completed.
この反応溶液を減圧蒸留すると、ICBHに塩化水素が
付加しt化合物が沸点79.5〜86.0℃715mm
Hgの範囲に122.7f(収率94.1%)得られる
。When this reaction solution is distilled under reduced pressure, hydrogen chloride is added to ICBH and the t compound has a boiling point of 79.5-86.0℃715mm
122.7f (yield 94.1%) was obtained in the Hg range.
この化合物を、Po1yeater FF (101)
のカラムを用いてGo分析すると、4つのピークに分か
れ、4種の異性体混合物でろる事が判った。This compound was converted into Polyyeater FF (101)
Go analysis using a column revealed that it was divided into four peaks and consisted of a mixture of four isomers.
ピーク1(Gc比):6011
ピーク2(1):20チ
ピーク3(1):15饅
ピーク4(1): 5%
”C−NMR(ODOJ8溶媒、TM8内部標準、δC
2多重度):
”0−NMR分析では、化合物(Dに相当するピークは
検出されなかった。tた、主生成物でろるピーク1及び
ピーク2に相当する化合物はそれぞれ次式0GV)及び
(ff)で界わされる化合物でわると推定された。Peak 1 (Gc ratio): 6011 Peak 2 (1): 20 Peak 3 (1): 15 Peak 4 (1): 5% C-NMR (ODOJ8 solvent, TM8 internal standard, δC
2 multiplicity): In the 0-NMR analysis, no peak corresponding to compound (D was detected. In addition, the compounds corresponding to peak 1 and peak 2, which are the main products, have the following formulas 0GV) and (0GV) and ( ff).
(Xll/) (XV)
ピーク1:
14.1(Q ) 、 34.6(t)、 36.0(
t)、 36.8(d)。(Xll/) (XV) Peak 1: 14.1(Q), 34.6(t), 36.0(
t), 36.8(d).
42.8(t)、546(a)、61.2(d)、11
6.7((1)。42.8(t), 546(a), 61.2(d), 11
6.7 ((1).
141.2(s)
ピーク2:
10.0((1)、36.0 (t )、42.5(t
)、44.0(t)。141.2(s) Peak 2: 10.0((1), 36.0(t), 42.5(t
), 44.0(t).
49.0(d)、 54.6(d)、81.2(s )
、 133.3(a)。49.0(d), 54.6(d), 81.2(s)
, 133.3(a).
xa9.2(a) 以上xa9.2(a) that's all
Claims (1)
がエキソ又はエンドでろること金示す) で表わされる1−エチル−3−ハロゲノ−トリシクロ[
2,2,1,oz、g)ヘゲタン。 2一般式([0 で表わされるエチリデンビシクロヘゲテンを溶媒中又は
無溶媒で次式 (式中、XはC!又ij Brを示す)で表わされるハ
ロゲン化水素酸と反応させることt−特徴とする次式(
1) (式中、又は前記と同じ。波線9〜は置換位置がエキソ
又はエンドであることを示す)で表わされるl−エチル
−3−ハロゲノ−トリシクロ(2,2,1,0”・6〕
ヘゾタンの製造法。[Claims] 1. 1-ethyl-3-halogeno-tricyclo [
2,2,1,oz,g) Hegetan. 2. Reacting ethylidene bicyclohegetene represented by the general formula ([0) with a hydrohalic acid represented by the following formula (wherein, X represents C! or ij Br) in a solvent or without a solvent. The following formula (
1) l-ethyl-3-halogeno-tricyclo(2,2,1,0".6 ]
Manufacturing method of hezotan.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11156184A JPS60255740A (en) | 1984-05-31 | 1984-05-31 | 1-ethyl-3-halogeno-tricyclo(2.2.1.02,6)heptane and its preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11156184A JPS60255740A (en) | 1984-05-31 | 1984-05-31 | 1-ethyl-3-halogeno-tricyclo(2.2.1.02,6)heptane and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60255740A true JPS60255740A (en) | 1985-12-17 |
JPH0410453B2 JPH0410453B2 (en) | 1992-02-25 |
Family
ID=14564498
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11156184A Granted JPS60255740A (en) | 1984-05-31 | 1984-05-31 | 1-ethyl-3-halogeno-tricyclo(2.2.1.02,6)heptane and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60255740A (en) |
-
1984
- 1984-05-31 JP JP11156184A patent/JPS60255740A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH0410453B2 (en) | 1992-02-25 |
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