Aldehyde and ketone syntheses using methylthiomethyl p-tolyl sulfone

Tetrahedron Letters,Vo1.26,No.20,pp Printed in Great Britain

ALDEHYDE

AND KETONE

Katsuyuki

Ogura*,

Yahata, Department Chiba

Abstract: give mono-

Kazuo

Kazumasa

USING

University,

Faculty

l-33, Chiba

sulfone

products

SULFONE

Nobuhiro

Iida

of Engineering, 260,

Japan

(1) was conveniently

(2 and 4).

of 2 and 4 into aldehydes

p-TOLYL

Nakamura,

and Hirotada

Chemistry,

p-tolyl

and dialkylated

Masami

Takahashi,

Yayoicho

0040-4039/85 $3.00 + .Oo 01985 Pergamon Press Ltd.

METHYLTHIOMETHYL

Ohtsuki,

of Synthetic

Methylthiomethyl

trasformation were

SYNTHESES

2455-2458,1985

Reaction

(3) and ketones

alkylated

conditions

to

for the

(5), respectively,

exploited.

Our previous could

be utilized

papers

showed

that methylthiomethyl

p-tolyl

sulfone

(1)l

of carboxylic esters from alkyl halides, 3 from carboxylic esters, S-methyl-a-ketocarbothioates2 and carbaldehydes 2 cyclic ketones from l,n-dihaloalkanes, and a-alkoxy-e-arylacetic esters from 2 aromatic carbaldehydes. In this letter, we wish to report that 1 also is useful

for preparing

summarizes mono-

in the preparation

aldehydes

the present

and dialkylated

dithioacetal

S,S-dioxide

,SCH, cH2

pathways: products

'S02Tol

group

and ketones. Alkylation

The accompanying of 1 to give

the corresponding

(2 and 4) and the subsequent

hydrolysis

of the

of 2 and 4 are comprised.

,SCH,

RIX

b RICH 50%aqNaOH-Toluene 'S02Tol (TOMAC)

1

scheme

hv

*

R'CHO

(820) 3

2

I R2X

NaH/DMF I

[To1 = p-tolyl]

RI 'c=o R2'

H+ or hV (H20)

Compared

methods

their

with the conventional S-oxides, 485 the present

one has two distinct

alkylation

of 1 utilizes

an inexpensive

using

formaldehyde

and easily-handled

2455

dithioacetals

features:

and

(i) the

base

and

(ii) the

2

2456

hydrolysis possible

of 2 and 4 can be conducted to prepare

aldehydes

under

and ketones

basic

with

conditions

which

acid-sensitive

make

it

fuctional

group(s). As already

reported,

1 can generate

so easily

that monoalkylation

so-called

"two-phase

methylammonium have

found

of 1 with

reaction"

chloride

using

(TOMAC)

that NaH can cleanly

in DMF to produce

(4) in the reaction

of this

fact with

at its methylene

halide

50% aq. NaOH

proceeds

as a base

abstract

of 2 at room

with

the proton which

the coexisting

temperature

gave the dialkylated

alkyl

halide.

The combination

S,S-dioxide

the acid-assisted hydrolysis of ketone dithioacetal groups 5,6 provides a convenient synthetic route leading to

symmetrical

and unsymmetrical

For the preparation alkyl

halide

and NaH

in DMF

after

hydrolysis.

being

Hence,

heated

cleavage capture

was

initiated

of 2 and 4 into bond

of the C-SO2

the subsequent

removal

these

dialkylation

product

results.

of 1 with

(2) resisted

an

(1:lO)

under

to exploit

a reflux

a new type When

of 2 and 4 is photochemically ion (6) with

of methanethiol

the above-

was quantitatively

3 and 5, respectively:

carbenium

hV

2 or4

1 summarized

direct

2 (R1= n-C 12H25)

in cone HCl-methanol

of the resulting

Table

is recommended.

Thus,

our investigation

the conversion

(5).

ketones,

the monoalkylated

To our surprise, mentioned

ketones

of symmetrical

the

and trioctyl2 Further, we

catlyst.

carbanion,

carbon

under

as a phase-transfer

the corresponding

product

a carbanion an alkyl

moiety

water

recovered for 24 h.

of reaction

for

heterolytic

forced

to take place,

or hydroxide

produce

even

anion

and

3 and 5.

l

TolSO; 6

[Y=H

I

or R2]

R:C/sc”3

R1 'c=o Y' 3 or 5

l

Y"OSOTo1

When

a solution

with

a low-pressure

reaction

of 2 (R1= n-C12Hz5)

took place

give tridecanal

Hg arc lamp

in the presence

(3: R1= n-C 12H25).

sulfonyl-l-(methylthio)tridecane photochemical p-tolyl

group.

influenced

transformation Since

(19:l)

a Vycor

or absence Under

remained

was

filter,

of a base

unchanged,

formation

irradiated a smooth

(NaHC03

the same conditions,

of 2 is initiated

the photolytic

by oxygen-bubbling

in dioxane-water

(10 W) through

indicating

by the light

of ethanol

to

that the

absorption

of 3 (R1= n-C12H25)

and the employment

or NaOH)

l-methyl-

of the

was not

as a solvent

2457 Table 1.

Ketone Synthesis Using 1

Starting

Alkyl Halide

Material

(equiv)

2; R=PhCH,

CH,I (3.1)

[A] rt/19

[D] reflux/Z

2; R=PhCH,

n-CsH1sBr(2.0)

[A] rt/48 +50/3

PI

2; R=CH3

PhCH,Br (1.5)

[A] rt/48+60/3

Alkylationa

Hydrolysisb

Temp(oC)/Time(h)

Overall

Temp/Time(h) Yield 96%

reflux/3

92%

85%

CH,I (2.4)

[A] rt/42

[El reflux/3 [Dl reflux/3

1

PhCH2Br (2.3)

[BJ rt/48*60/3

[E] reflux/3

74%

1

n-C12Hz5Br(2.6) [B] rt/48 * SO/3

[El reflux/3 [D] reflux/3

93%

2;

R=n-C,,H,,

90%

1

Br(CH,)5Br(1.0) [C] 60/144

1

Br(CH2)4Br(1.0) [C] 60/96

91%c

PI

1

Br(CH,),Br(1.1) [B] -15/6 +rt/18

[F] 100 'C/20

reflux/S

98%' 83%

a(AI: with NaH (1.3 equiv)/DMF, (BI: with NaH (2.5 equiv)/DME', [Cl: with TOMAC (0.02 equiv)/toluene-50%aqNaOH. b[Dl: with cone HCl/MeOH (0.3-l/10 v/v), (El: with cone H2S04/MeOH (0.5-l/10 v/v). (Fl: withconcHCl/dioxane (l/10 v/v). 'ref. 2.

Table 2.

Photo-induced Hydrolysis of 2 and 4a

R1

R2

Solvent

Baseb Atmosphere ___

2; n-Cl,H25

-

Dioxane

2; n-C12H25

-

Dioxane-H20

2; n-C12H25

-

Dioxane-H20 (19:l) NaHC03

2; n-C,,H,,

-

Dioxane-H20 (19:l) NaHC03

N, (19:l)

---

N,

2; n-C12H25

-

EtOH-H,O (19:l)

2; n-C12H25

-

Dioxane-H20

(19:l) NaOH

2; 4-ClC,H,

-

Dioxane-H20

(19:l) NaHC03

Dioxane-H20

(19:l) NaHC03

Dioxane-H20

(19:l) NaOH

4; n-Cr2H25 CH3 4; n-C12H25 CH, 4;

-W2)5-

N, O2

NaHC03

N2 N2 N2

3or 5

2or4(

)'

26%d

29%

67%

28%

(93%)

61%

25%

(82%)

63%

0%

(36%)

24%e

31%

72%

18%

(89%)

20%

35%

(33%)

46sf

__g

N2

58%h

__g

67ti

__g

N2

Dioxane-H20 (19:l) NaHC03

N2

'a solution of 2 or 4 (-500 n&ZOO ml) was irradiated with a low-pressure Hg arc lamp (10 W) through a Vycor filter under being externally cooled with water. bthree equiv to 2 or 4. 'the yield of 3 based on the unrecovered 2. dthe trioxane derivative of tridecanal (33%) was also obtained. e7 (38%) was gormed. f2-methylthio-l:tetradecene (8) was given in 29% yield. gnot determined. 8 (28%) was produced. "trapped as its 2,4dinitrophenylhydrazone. ,SCI-I, ,SCH,

n-C12H2,CH 'OEt

produced

1-ethoxy-1-(methylthio)tridecane

transformation

heterolytic

of 2 into 4 might fission

of the C-SO2

involve bond.

(7),

7

n-C12H25C~CH

8 2

the

the cation

photochemical

(6) produced

At the present

time,

by the

we cannot

exclude

2458

the

possibility

that

sulfinato)alkane In the similar

given

hydrolysis

group

ketones

(5) were

of 6 and p-toluenesulfinate

to afford

the corresponding

applicable

as shown

in Table

for the hydrolysis

in the presence

are susceptible

l-methylthio-l-(p-toluene-

afforded

a new method

can be conducted

which

via

developed

1 to 3 and 5 are suitably ketones

formed

by the recombination

manner,

Thus we have S,S-dioxide

3 is partially

carbonyl

Since

the present

to the preparation

to an acid,

of a dithioacetal

group.

of a base,

of aldehydes

A few examples

anion.

2.

are shown

this routes

from

and in the

following.

c,

Nan

0-(CH,),Cl + 1~

0

DMF

,SCH,

Q-

0-(CH,),CH 'SO,Tol L

(rt)

I

n-C5HlIBr

@-

a

L (HZo)

@- 0

93%

0-(CH,),CHO 67%(78%)b

NaH/DMF (rt-60°c)

O-(CH,),,

,SCH,

0-W214

hv a

0

;c=o

n-CgHl
(HZO)

n-C5H11 50%

SCH,

Nan

+ 1

l

SOzTol

DMP

Cl (rt-60°C)

,:",, + 2

83%(93%)b

62%

awithalow-pressurexg arclamp (Vycor filter) indioxane-H 3 eqUiVOfNaHC03.

ketone

syntheses

using

hydrolysis

0 (19:l) containing

bbasedontheunrecoveredstartingmater?al.

Now we are investigating

photo-induced

00O

the scopes

1, and a detailed of dithioacetal

and limitation

of the aldehyde

mechanistic

study

S,S-dioxide

groups

and

on the is our on-going

subject.

References

and Footnotes

1) This reagent (1) can be conveniently prepared from dimethyl sulfoxide: K. Ogura, N. Yahata, J. Watanabe, K. Takahashi, and H. Iida, Bull. Chem. Sot. Jpn., 56, 3543 (1983). Now 1 is commercially available from Nissan Chemical Industries Ltd. 2) K. Ogura, N. Yahata, K. Hashizume, K. Tsuyama, K. Takahashi, and H. Iida, Chem. Lett., 1983, 767. 3) K. Ogura, N. Yahata, K. Takahashi, and H. Iida. Tetrahedron Lett., 24, 5761 (1983). 4) Formaldehyde diethyl dithioacetal: 3. F. Arens, M. Fr8ling. and A. Fr8ling. Rec. Trav. Chim. Pays-gas, 78, 663 (1959); A. Fr8ling and J. F. Arens, Rec. Trav. Chim. Pays-gas, 81, 1009 (1962). 1,3-Dithiane: D. Seebach, Synthesis, 1969, 17. Formaldehyde dimethyl dithioacetal S-oxide: K. Ogura and G. Tsuchiahsi, Tetrahedron Lett., 1971, 3151. Formaldehyde diethyl dithioacetal S-oxide: J. E. Richman, J. L. Herrmann, and R. H. Schlessinger, Tetrahedron &, 1973. 3267. 5) K. Ogura, M. Suzuki, 3. Watanabe, M. Yamashita, H. Iida, and G. Tsuchihashi, Chem. Lett., 1982, 813. 6) Y. Murata, K. Inomata, H. Kinoshita, and H. Kotake, Bull. Chem. Sot. Jpn., 56, 2539 (1983).

(Received in Japan 21 February 1985)