JPH0376313B2 - - Google Patents
Info
- Publication number
- JPH0376313B2 JPH0376313B2 JP62052748A JP5274887A JPH0376313B2 JP H0376313 B2 JPH0376313 B2 JP H0376313B2 JP 62052748 A JP62052748 A JP 62052748A JP 5274887 A JP5274887 A JP 5274887A JP H0376313 B2 JPH0376313 B2 JP H0376313B2
- Authority
- JP
- Japan
- Prior art keywords
- thione
- oxathiolane
- carbon disulfide
- diothylane
- yield
- 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.)
- Expired - Lifetime
Links
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 54
- HXOYEKUNPUDUPM-UHFFFAOYSA-N 1,3-oxathiolane-2-thione Chemical class S=C1OCCS1 HXOYEKUNPUDUPM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000000262 chemical ionisation mass spectrometry Methods 0.000 description 9
- 150000002924 oxiranes Chemical class 0.000 description 8
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 4
- UDYVVASQSGTSCZ-UHFFFAOYSA-N 5-hexyl-1,3-oxathiolane-2-thione Chemical compound CCCCCCC1CSC(=S)O1 UDYVVASQSGTSCZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- JMQUTNXASHHDAD-UHFFFAOYSA-N 5,5-dimethyl-1,3-oxathiolane-2-thione Chemical compound CC1(C)CSC(=S)O1 JMQUTNXASHHDAD-UHFFFAOYSA-N 0.000 description 2
- QRPNHWWWYYYOGC-UHFFFAOYSA-N 5-ethyl-1,3-oxathiolane-2-thione Chemical compound CCC1CSC(=S)O1 QRPNHWWWYYYOGC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 2
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 2
- WJJSZTJGFCFNKI-UHFFFAOYSA-N 1,3-oxathiolane Chemical compound C1CSCO1 WJJSZTJGFCFNKI-UHFFFAOYSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- PQWDATLZEFPKGE-UHFFFAOYSA-N 2-sulfanylideneoxathiolane Chemical compound S=S1CCCO1 PQWDATLZEFPKGE-UHFFFAOYSA-N 0.000 description 1
- YXQDJSKSXLWHFQ-UHFFFAOYSA-N 4-hexyl-1,3-dithiolane-2-thione Chemical compound CCCCCCC1CSC(=S)S1 YXQDJSKSXLWHFQ-UHFFFAOYSA-N 0.000 description 1
- UNAVLWYSWPISLX-UHFFFAOYSA-N 4-phenyl-1,3-dithiolane-2-thione Chemical compound S1C(=S)SCC1C1=CC=CC=C1 UNAVLWYSWPISLX-UHFFFAOYSA-N 0.000 description 1
- YPXQSGWOGQPLQO-UHFFFAOYSA-N 5-nitro-1,3-dihydrobenzimidazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2N=C(S)NC2=C1 YPXQSGWOGQPLQO-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- -1 reaction time Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- LVBXEMGDVWVTGY-UHFFFAOYSA-N trans-2-octenal Natural products CCCCCC=CC=O LVBXEMGDVWVTGY-UHFFFAOYSA-N 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は１，３−ジオチラン−２−チオン誘導
体及び１，３−オキサチオラン−２−チオン誘導
体の製造方法に関するもので、より詳細にはこれ
らの化合物を、エポキシド類と二硫化炭素とを塩
基の存在下に2000〜8000Kg／cm2の高圧で反応させ
ることにより簡単にかつ収率よく製造する方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 1,3-diothylane-2-thione derivatives and 1,3-oxathiolane-2-thione derivatives. The present invention relates to a method for producing easily and with high yield by reacting carbon disulfide with carbon disulfide in the presence of a base at a high pressure of 2,000 to 8,000 kg/cm 2 .
（産業上の利用分野）
従来、１，３−ジオチラン−２−チオン誘導体
には、電荷移動錯体であるTTF（テトラチアフル
バレン）と合成中間体としての利用が多数知られ
ており、また近年では生理活性物質の中間材料と
しての利用も多数報告されている。U.S.4131683、
Berg.876202U.S.4172941、U.S.4206119）。１，３
−オキサチオラン−２−チオン誘導体は、１，３
−ジチオラン−２−チオンの誘導体の１個の硫黄
を酸素におきかえた類似化合物であり、同様の利
用が期待される。(Industrial Application Field) Many 1,3-diothylane-2-thione derivatives have been known to be used as synthetic intermediates with TTF (tetrathiafulvalene), which is a charge transfer complex, and in recent years, There have also been many reports of its use as an intermediate material for physiologically active substances. US4131683,
Berg.876202U.S.4172941, US4206119). 1,3
-Oxathiolane-2-thione derivative is 1,3
It is a similar compound of the -dithiolane-2-thione derivative in which one sulfur is replaced with oxygen, and is expected to be used in the same way.
（発明が解決しようとする問題点）
このように１，３−ジオチラン−２−チオンの
誘導体は有用な化合物であるが、現在の合成法は
操作が複雑であり、精製が困難な場合もある。こ
のため発明者らは高圧下においてチイランと二硫
化炭素とを反応させ高収率で、１，３−ジオチラ
ン−２−チオン誘導体を合成する反応を開発した
（61年願49366号、Bull.Chem.Soc.Jpn.、60727
（1987））。しかしチイランは一般的にエポキシド
から合成されるためエポキシドと二硫化炭素から
直接１，３−ジオチラン−２−チオンの誘導体を
合成できればより効率的である。(Problems to be Solved by the Invention) As described above, derivatives of 1,3-diothyrane-2-thione are useful compounds, but the current synthesis methods are complicated and purification is sometimes difficult. . Therefore, the inventors developed a reaction to synthesize 1,3-diothyrane-2-thione derivatives in high yield by reacting thiirane and carbon disulfide under high pressure (1961 Application No. 49366, Bull.Chem .Soc.Jpn., 60727
(1987)). However, since thiirane is generally synthesized from epoxide, it would be more efficient if 1,3-diothyrane-2-thione derivatives could be synthesized directly from epoxide and carbon disulfide.
１，３−オキサチオラン−２−チオン誘導体の
合成法としてはすでにエポキシドと二硫化炭素か
らの合成法が報告されているが、常圧においては
かさ高い置換基を有するエポキシドを用いた場
合、反応速度が遅く収率が低いという欠点があつ
た。 As a synthesis method for 1,3-oxathiolane-2-thione derivatives, a synthesis method from epoxide and carbon disulfide has already been reported, but at normal pressure, when an epoxide with a bulky substituent is used, the reaction rate is low. The disadvantage was that the process was slow and the yield was low.
したがつて本発明の目的は１，３−ジオチラン
−２−チオン誘導体、あるいは１，３−ジオチラ
ン−２−チオンの誘導体と１，３−オキサチオラ
ン−２−チオンの誘導体の両者の効率的な製造方
法を開発することである。 Therefore, an object of the present invention is to efficiently produce 1,3-diothylane-2-thione derivatives or both 1,3-diothylane-2-thione derivatives and 1,3-oxathiolane-2-thione derivatives. The goal is to develop methods.
（問題点を解決するための手段）
本発明者らは2000〜8000Kg／cm2の条件下にエポ
キシド１と二硫化炭素とを塩基の存在下反応させ
ることにより、１，３−ジオチラン−２−チオン
の誘導体２を高収率で製造できることを見出し、
また触媒、反応時間、溶媒などを選択することに
より１，３−ジオチラン−２−チオンの誘導体２
及び１，３−オキサチオラン−２−チオンの誘導
体３の両者を同時に効率よく製造できることを見
出し、本発明を完成するに至つた。(Means for solving the problem) The present inventors reacted epoxide 1 and carbon disulfide in the presence of a base under conditions of 2000 to 8000 Kg/cm 2 to obtain 1,3-diothyrane-2- discovered that thione derivative 2 could be produced in high yield,
In addition, by selecting the catalyst, reaction time, solvent, etc., the derivative 2 of 1,3-diothyrane-2-thione can be prepared.
and 1,3-oxathiolane-2-thione derivative 3 can be efficiently produced at the same time, leading to the completion of the present invention.
すなわち本発明は
一般式
（式中、R1はアルキル基またはアリール基、
R2R3はアルキル基又は水素原子を表わす。）
で示されるエポキシドと二酸化炭素とを塩基の存
在下、2000〜8000Kg／cm2の高圧をかけて反応させ
ることを特徴とする
一般式
（式中R1、R2、及びR3は前記と同じ意味をもつ）
で示される１，３−ジオチラン−２−チオンの誘
導体２及び１，３−オキサチオラン−２−チオン
の誘導体３の製造方法を提供するものである。 That is, the present invention is based on the general formula (In the formula, R 1 is an alkyl group or an aryl group,
R 2 R 3 represents an alkyl group or a hydrogen atom. ) A general formula characterized by reacting the epoxide shown in (In the formula, R 1 , R 2 , and R 3 have the same meanings as above)
The present invention provides a method for producing 1,3-diothylane-2-thione derivative 2 and 1,3-oxathiolane-2-thione derivative 3 shown in the following.
本発明の出発原料であるエポキシド化合物１は
多種のものが市販されており、二硫化炭素も安価
に市販されている。したがつて、化合物１を適宜
に選択することによりR1、R2、及びR3について
の所望の置換基を導入した任意の１，３−ジオチ
ラン−２−チオンの誘導体及び１，３−オキサチ
オラン−２−チオンの誘導体を製造することがで
きる。なお本発明においてR1〜R3は反応に不活
性な置換基でさらに置換されている場合も包含す
る。 Various types of epoxide compound 1, which is the starting material of the present invention, are commercially available, and carbon disulfide is also commercially available at low cost. Therefore, any 1,3-diothylane-2-thione derivative and 1,3-oxathiolane in which desired substituents for R 1 , R 2 , and R 3 are introduced by appropriately selecting Compound 1 Derivatives of -2-thione can be produced. In the present invention, R 1 to R 3 also include cases where they are further substituted with a substituent inert to the reaction.
次に本発明における目的化合物２及び３の生成
経路を塩基としてトリエチルアミンを用いた１−
オクテンオキシドと二硫化炭素との反応を例にと
れば下記の式４のように表現できる。 Next, the production route of the target compounds 2 and 3 in the present invention was modified using triethylamine as a base.
Taking the reaction between octene oxide and carbon disulfide as an example, it can be expressed as the following equation 4.
本発明の反応は通常、第三級アミン触媒の存在
下にて高圧条件下で行われる、例えばトリエチル
アミン、ピリジン等が触媒として用いられた。圧
力は高圧ほど好ましいが、一般には500〜9000
Kg／cm2の範囲で選択される。反応温度は特に制約
されないが副反応の進行を抑制する意味では室温
〜120℃の温度の採用が好ましい。反応時間は圧
力、温度等に左右されるが、通常５〜50時間で十
分である。 The reaction of the present invention is usually carried out under high pressure conditions in the presence of a tertiary amine catalyst, for example triethylamine, pyridine, etc., were used as catalysts. The higher the pressure, the better, but generally 500 to 9000
Selected in the range of Kg/ cm2 . Although the reaction temperature is not particularly limited, it is preferable to use a temperature between room temperature and 120°C in order to suppress the progress of side reactions. The reaction time depends on pressure, temperature, etc., but usually 5 to 50 hours is sufficient.
反応混合物から過剰の二硫化炭素及び溶媒を留
去したのち減圧蒸留もしくは再結晶することによ
り本発明の目的化合物が収率よく得られる。かく
して得られた目的化合物は必要に応じてカラムク
ロマトグラフイーにより分離し、各純粋物のIR、
NMR、GCを分析することによりその製造を確
認できる。 The target compound of the present invention can be obtained in good yield by distilling off excess carbon disulfide and the solvent from the reaction mixture, followed by distillation under reduced pressure or recrystallization. The target compounds thus obtained are separated by column chromatography as necessary, and each pure product is analyzed by IR,
Its production can be confirmed by NMR and GC analysis.
（発明の効果）
本発明によれば、従来法では合成操作が複雑で
ある、あるいは反応速度が遅く収率が低いなどの
問題点がある１，３−ジオチラン−２−チオンの
誘導体及び１，３−オキサチオラン−２−チオン
の誘導体類を種々の置換体が容易に入手できるエ
ポキシドの二硫化炭素を用いて一段階で高収率か
つ効率的に製造することができる。(Effects of the Invention) According to the present invention, 1,3-diothylane-2-thione derivatives and 1, Derivatives of 3-oxathiolane-2-thione can be produced in high yield and efficiently in one step using carbon disulfide, an epoxide in which various substituents are readily available.
（実施例）
次に本発明を実施例に基づきさらに詳細に説明
する。(Examples) Next, the present invention will be described in more detail based on Examples.
実施例 １
テフロンチユーブに１−オクテンオキシド0.64
ｇ、トリエチルアミン0.05ｇ及び二硫化炭素3.80
ｇを封入し、高圧反応装置に入れて2000Kg／cm2に
加圧し100℃で20時間反応した。圧を常圧に戻し
たのち反応物をとり出し、過剰の二硫化炭素を留
去した。残留物を減圧蒸留することにより５−ヘ
キシル−１，３−オキサチオラン−２−チオンを
56.9％、４−ヘキシル−１，３−ジオチラン−２
−チオンを27.3％の収率で得た。これらの化合物
はシリカゲルを用いたカラムクロマトグラフイー
（ヘキサン：クロロホルム１：１）によりそれぞ
れを単離し、構造を確認した。Example 1 1-octene oxide 0.64 in Teflon tube
g, triethylamine 0.05 g and carbon disulfide 3.80 g
g was sealed and placed in a high-pressure reactor, pressurized to 2000 Kg/cm 2 and reacted at 100°C for 20 hours. After the pressure was returned to normal pressure, the reactant was taken out, and excess carbon disulfide was distilled off. 5-hexyl-1,3-oxathiolane-2-thione was obtained by distilling the residue under reduced pressure.
56.9%, 4-hexyl-1,3-diothyrane-2
-thione was obtained in a yield of 27.3%. These compounds were each isolated by column chromatography using silica gel (hexane:chloroform 1:1), and their structures were confirmed.
５−ヘキシル−１，３−オキサチオラン−２−チ
オン
IR；1189cm-1、1048cm-1
CI−MSによるQM+；205
NMR；0.89（ｔ、3H、CH3）、1.32（Ｓ、8H、
（CH2）4）、3.35−3.80（ｍ、2H、CH2）、4.95−
5.35（ｍ、1H、CH）
４−ヘキシル−１，３−ジオチラン−２−チオン
IR；1065cm-1
CI−MSによるQM+；221
NMR；0.88（ｔ、3H、CH3）、1.32（Ｓ、8H
（CH2）4）、1.66−2.15（ｍ、2H、CH2）、3.55−
4.15（ｍ、2H、CH2）、4.23−4.60（ｍ、1H、
CH）
同様の反応をオートクレーブ中、常圧で行うと
５−ヘキシル−１，３−オキサチオラン−２−チ
オンは16.7％、４−ヘキシル−１，３−ジチオラ
ン−２−チオンの収率は0.9％のみであつた。5-hexyl-1,3-oxathiolane-2-thione IR; 1189 cm -1 , 1048 cm -1 QM + by CI-MS; 205 NMR; 0.89 (t, 3H, CH 3 ), 1.32 (S, 8H,
(CH 2 ) 4 ), 3.35−3.80 (m, 2H, CH 2 ), 4.95−
5.35 (m, 1H, CH) 4-hexyl-1,3-diothyrane-2-thione IR; 1065 cm -1 QM + by CI-MS; 221 NMR; 0.88 (t, 3H, CH 3 ), 1.32 (S, 8H
(CH 2 ) 4 ), 1.66−2.15 (m, 2H, CH 2 ), 3.55−
4.15 (m, 2H, CH 2 ), 4.23−4.60 (m, 1H,
CH) When a similar reaction is carried out in an autoclave at normal pressure, the yield of 5-hexyl-1,3-oxathiolane-2-thione is 16.7% and the yield of 4-hexyl-1,3-dithiolane-2-thione is 0.9%. It was only.
実施例 ２
前記と同様にして１−オクテンオキシド0.64
ｇ、トリエチルアミン0.05ｇ、及び二硫化炭素
1.90ｇを8000Kg／cm2、100℃で20時間反応させた。
前記と同様の処理により５−ヘキシル−１，３−
オキサチオラン−２−チオンは4.9％、４−ヘキ
シル−１，３−ジオチラン−２−チオンを70.6％
の収率で得た。Example 2 1-octene oxide 0.64 in the same manner as above
g, triethylamine 0.05 g, and carbon disulfide
1.90g was reacted at 8000Kg/cm 2 and 100°C for 20 hours.
5-hexyl-1,3-
4.9% oxathiolane-2-thione, 70.6% 4-hexyl-1,3-diothylane-2-thione
It was obtained in a yield of .
実施例 ３
前記と同様にして１−オクテンオキシド0.64g、
Ｎ−メチルモルホリン0.05ｇ、及び二硫化炭素
1.90ｇを8000Kg／cm2、100℃で20時間反応させた。
前記と同様の処理により５−ヘキシル−１，３−
オキサチオラン−２−チオンは30.4％、４−ヘキ
シル−１，３−ジオチラン−２−チオンを45.5％
の収率で得た。Example 3 0.64 g of 1-octene oxide in the same manner as above,
0.05g of N-methylmorpholine and carbon disulfide
1.90g was reacted at 8000Kg/cm 2 and 100°C for 20 hours.
5-hexyl-1,3-
Oxathiolane-2-thione is 30.4%, 4-hexyl-1,3-diothylane-2-thione is 45.5%
It was obtained in a yield of .
実施例 ４
前記と同様にしてプロピレンオキシド0.29ｇ、
トリエチルアミン0.05ｇ、及び二硫化炭素1.90ｇ
を8000Kg／cm2、100℃で20時間反応させた。前記
と同様の処理により４−メチル−１，３−ジオチ
ラン−２−チオンを82.7％の収率で得た。Example 4 0.29 g of propylene oxide in the same manner as above,
Triethylamine 0.05g and carbon disulfide 1.90g
was reacted at 8000Kg/cm 2 and 100°C for 20 hours. 4-Methyl-1,3-diothylane-2-thione was obtained in a yield of 82.7% by the same treatment as above.
４−メチル−１，３−ジオチラン−２−チオン
IR；1076cm-1、1050cm-1、1033cm-1
CI−KSによるQM+；151
NMR；1.64（ｄ、3H、CH3）、3.55−3.85（dd、
1H、CH2の１プロトン）、3.95−4.20（dd、1H、
CH2の１プロトン）、4.35−4.75（ｍ、1H、CH）
実施例 ５
前記と同様にしてブチレンオキシド0.36ｇ、Ｎ
−メチルモルホリン0.05ｇ、及び二硫化炭素1.90
ｇを8000Kg／cm2、70℃で20時間反応させた。前記
と同様の処理により５−エチル−１，３−オキサ
チオラン−２−チオン20.3％、４−エチル−１，
３−ジオチラン−２−チオンを36.6％の収率で得
た。4-Methyl-1,3-diothylane-2-thione IR; 1076 cm -1 , 1050 cm -1 , 1033 cm -1 QM + by CI-KS; 151 NMR; 1.64 (d, 3H, CH 3 ), 3.55-3.85 ( dd,
1H, 1 proton of CH2 ), 3.95−4.20 (dd, 1H,
1 proton of CH 2 ), 4.35-4.75 (m, 1H, CH) Example 5 Butylene oxide 0.36 g, N
- 0.05 g of methylmorpholine and 1.90 g of carbon disulfide
8000Kg/cm 2 and 70°C for 20 hours. By the same treatment as above, 20.3% of 5-ethyl-1,3-oxathiolane-2-thione, 4-ethyl-1,
3-diothylane-2-thione was obtained with a yield of 36.6%.
５−エチル−１，３−オキサチオラン−２−チオ
ン
IR；1188cm-1
CI−MSによるQM+；149
NMR；1.09（ｔ、3H、CH3）、1.53−2.20（ｍ、
2H、CH2）、3.50−3.74（ｍ、2H、CH2）、4.90
−5.28（ｍ、1H、CH）
４−エチル−１，３−ジオチラン−２−チオン
IR；1049cm-1、1083cm-1
CI−MSによるQM+；165
NMR；1.07（ｔ、3H、CH3）、1.60−2.20（ｍ、
2H、CH2）、3.40−4.20（ｍ、2H、CH2）、4.20
−4.55（（ｍ、1H、CH）
実施例 ６
前記と同様にしてイソブチレンオキシド0.72
ｇ、Ｎ，Ｎ−ジメチルエチルアミン0.07ｇを8000
Kg／cm2、100℃で20時間反応させた。前記と同様
の処理により、５，５−ジメチル−１，３−オキ
サチオラン−２−チオンは66.9％、４，４−ジメ
チル−１，３−ジオチラン−２−チオンを17.7％
の収率で得た。5-Ethyl-1,3-oxathiolane-2-thione IR; 1188 cm -1 QM + by CI-MS; 149 NMR; 1.09 (t, 3H, CH 3 ), 1.53-2.20 (m,
2H, CH 2 ), 3.50−3.74 (m, 2H, CH 2 ), 4.90
-5.28 (m, 1H, CH) 4-ethyl-1,3-diothyrane-2-thione IR; 1049 cm -1 , 1083 cm -1 QM + by CI-MS; 165 NMR; 1.07 (t, 3H, CH 3 ) , 1.60−2.20(m,
2H, CH 2 ), 3.40−4.20 (m, 2H, CH 2 ), 4.20
−4.55 ((m, 1H, CH) Example 6 Isobutylene oxide 0.72 in the same manner as above
g, N,N-dimethylethylamine 0.07g to 8000
Kg/cm 2 and reacted at 100°C for 20 hours. By the same treatment as above, 5,5-dimethyl-1,3-oxathiolane-2-thione was reduced to 66.9% and 4,4-dimethyl-1,3-diothylane-2-thione was reduced to 17.7%.
It was obtained in a yield of .
５，５−ジメチル−１，３−オキサチオラン−２
−チオン
IR；1252cm-1、1127cm-1
CI−MSによるQM+；149
NMR；1.67（ｓ、6H、2CH3）、3.48（ｓ、2H、
CH2）
４，４−ジメチル−１，３−ジオチラン−２−
チオン
IR；1056cm-1、1086cm-1
CI−MSによるQM+；165
NMR；1.73（ｓ、6H、2CH3）、3.74（ｓ、2H、
CH2）
実施例 ７
前記と同様にしてスチレンオキシド1.20ｇ、ピ
リジン0.08ｇ、及び二硫化炭素3.80ｇを8000Kg／
cm2、100℃で20時間反応させた。過剰の二硫化炭
素を留去したのちエタノールを再結晶することに
より92.9％、の収率で４−フエニル−１，３−ジ
チオラン−２−チオンを得た。5,5-dimethyl-1,3-oxathiolane-2
-thione IR; 1252 cm -1 , 1127 cm -1 QM + by CI-MS; 149 NMR; 1.67 (s, 6H, 2CH 3 ), 3.48 (s, 2H,
CH2 ) 4,4-dimethyl-1,3-diothyrane-2-
Thione IR; 1056 cm -1 , 1086 cm -1 QM + by CI-MS; 165 NMR; 1.73 (s, 6H, 2CH 3 ), 3.74 (s, 2H,
CH 2 ) Example 7 In the same manner as above, 1.20 g of styrene oxide, 0.08 g of pyridine, and 3.80 g of carbon disulfide were added to 8000 kg/
cm 2 and reacted at 100°C for 20 hours. After distilling off excess carbon disulfide, ethanol was recrystallized to obtain 4-phenyl-1,3-dithiolane-2-thione in a yield of 92.9%.
４−フエニル−１，３−ジオチラン−２−チオン
IR；1047cm-1
CI−MSによるQM+；213
NMR；3.90−4.40（ｍ、2H、CH3）、5.55−5.80
（dd、1H、CH）、7.25−7.70（ｍ、5H、C6H5）
実施例 ８
前記と同様にしてシクロヘキセンオキシド0.49
ｇ、Ｎ−メチルモルホリン0.05ｇ、及び二硫化炭
素1.90ｇを8000Kg／cm2、70℃で20時間反応させ
た。過剰の二硫化炭素を留去したのちシリカゲル
を用いたカラムクロマトグラフイー（ヘキサン：
クロロホルム１：１）により４，５−テトラメチ
メン−１，３−オキサチオラン−２−チオンを
54.0％、４，５−テトラメチレン−１，３−ジオ
チラン−２−チオンを35.8％の収率で得た。4-phenyl-1,3-diothylane-2-thione IR; 1047 cm -1 QM + by CI-MS; 213 NMR; 3.90-4.40 (m, 2H, CH 3 ), 5.55-5.80
(dd, 1H, CH), 7.25-7.70 (m, 5H, C 6 H 5 ) Example 8 Cyclohexene oxide 0.49 in the same manner as above
g, 0.05 g of N-methylmorpholine, and 1.90 g of carbon disulfide were reacted at 8000 Kg/cm 2 and 70° C. for 20 hours. After distilling off excess carbon disulfide, column chromatography using silica gel (hexane:
4,5-tetramethymene-1,3-oxathiolane-2-thione with chloroform (1:1)
54.0%, 4,5-tetramethylene-1,3-diothylane-2-thione was obtained in a yield of 35.8%.
４，５−テトラメチレン−１，３−オキサチオラ
ン−２−チオン
CI−MSによるQM+；175
NMR；1.00−2.65（ｍ、8H、−（CH2）-4）、3.54−
4.00（ｍ、1H、CH）、4.13−4.65（ｍ、1H、
CH）
４，５−テトラメチレン−１，３−ジオチラン
−２−チオン
IR；1033cm-1
CI−MSによるQM+；191
NMR；1.00−2.40（ｍ、8H、−（CH2）-4）、3.90−
4.35（ｍ、2H、2CH）。4,5-tetramethylene-1,3-oxathiolane-2-thione QM + by CI-MS; 175 NMR; 1.00−2.65 (m, 8H, −(CH 2 ) −4 ), 3.54−
4.00 (m, 1H, CH), 4.13−4.65 (m, 1H,
CH) 4,5-tetramethylene-1,3-diothylane-2-thione IR; 1033 cm -1 QM + by CI-MS; 191 NMR; 1.00-2.40 (m, 8H, -(CH 2 ) -4 ), 3.90−
4.35 (m, 2H, 2CH).
Claims (1)
R3はアルキル基又は水素を表わす。） で示されるエポキシドと二硫化炭素とを塩基の存
在下、2000〜8000Kg／cm2の高圧にかけて反応させ
ることを特徴とする 一般式 【式】及び【式】 （式中R1、R2、及びR3は前記と同じ意味をもつ）
で示される１，３−ジオチラン−２−チオン誘導
体及び１，３−オキサチオラン−２−チオン誘導
体の製造方法。[Claims] 1. General formula (In the formula, R 1 is an alkyl group or an aryl group, R 2 ,
R 3 represents an alkyl group or hydrogen. ) is characterized by reacting the epoxide represented by the following with carbon disulfide in the presence of a base under high pressure of 2000 to 8000 Kg/ cm2 . and R 3 have the same meaning as above)
A method for producing a 1,3-diothylane-2-thione derivative and a 1,3-oxathiolane-2-thione derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62052748A JPS63218672A (en) | 1987-03-07 | 1987-03-07 | Production of 1,3-dithiolane-2-thione derivative and 1,3-oxathiolane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62052748A JPS63218672A (en) | 1987-03-07 | 1987-03-07 | Production of 1,3-dithiolane-2-thione derivative and 1,3-oxathiolane derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63218672A JPS63218672A (en) | 1988-09-12 |
| JPH0376313B2 true JPH0376313B2 (en) | 1991-12-05 |
Family
ID=12923530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62052748A Granted JPS63218672A (en) | 1987-03-07 | 1987-03-07 | Production of 1,3-dithiolane-2-thione derivative and 1,3-oxathiolane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218672A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7541319B2 (en) * | 2004-10-26 | 2009-06-02 | Chemtura Corporation | 1,3-dithiolane-2-thione additives for lubricants and fuels |
| JP5858212B2 (en) * | 2011-03-31 | 2016-02-10 | 和光純薬工業株式会社 | Method for producing cyclic trithiocarbonate |
-
1987
- 1987-03-07 JP JP62052748A patent/JPS63218672A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63218672A (en) | 1988-09-12 |
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